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Weakly Interacting Molecular Pairs: Unconventional Absorbers of Radiation in the Atmosphere pp 273–284Cite as

Spectroscopic and Thermochemical Information on the O2−O2 Collisional Complex Inferred From Atmospheric Uv/Visible O4 Absorption Band Profile Measurements

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Part of the book series: NATO Science Series ((NAIV,volume 27))

Abstract

Atmospheric profiles of the ultraviolet/visible (UV/vis) absorption bands of the collision complex O2−O2, or O4 in brief, are reported. The O4 absorption profiles are inferred from direct Sun spectra observed from the LPMA/DOAS (Laboratoire de Physique Moléculaire et Applications/Differential Optical Absorption Spectroscopy) balloon gondola. Seven O4 absorption bands — centered at ~ 360.7, 380.2, 446.7, 477.1, 532.2, 577.2, and 630.0 nm — are investigated for atmospheric pressures (p) ranging from ~ 500 hPa to ~ 40hPa and temperatures (T) ranging from 203 K to 250 K. For the encountered atmospheric conditions, it is found that, (a) the band shapes do not change with T and p and (b) the peak collision pair absorption intensities (αi) concurrently increase with decreasing T (by about 11% over a ΔT = 50K). That result is in agreement with previous laboratory O4 studies mostly conducted at high O2 partial pressures (up to several hundred bars). Furthermore, by reasonably assuming that the O4 absorption cross sections are T-independent, the inferred T-dependence of αi (T) suggests a thermally averaged enthalpy change <ΔH> = − (1207 ± 83) J/Mol involved in the formation of O4. Our inferred ΔH is in reasonable agreement with the orientation and spin averaged O4 well depth De(O4)(= − (1130 ± 80) J/Mol) measured in a recent O2−O2 collision experiment, when accounting for the rovibrational energy change during O4 formation (189 J/Mol).

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Author information

Authors and Affiliations

  1. Institut für Umweltphysik, INF 229, University of Heidelberg, D-69120, Heidelberg, Germany

    Klaus Pfeilsticker (Privatdozent), H. Bösch & R. Fitzenberger

  2. Laboratoire de Physique Moléculaire et Applications, Université Pierre et Marie Curie & CNRS, Paris, France

    Claude Camy-Peyret (director)

Authors
  1. Klaus Pfeilsticker
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  2. H. Bösch
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  3. R. Fitzenberger
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  4. Claude Camy-Peyret
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Editor information

Editors and Affiliations

  1. Université Pierre et Marie Curie & CNRS, Paris, France

    Claude Camy-Peyret

  2. Wave Research Center, General Physics Institute, Russian Academy of Sciences, Moscow, Russia

    Andrei A. Vigasin

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Pfeilsticker, K., Bösch, H., Fitzenberger, R., Camy-Peyret, C. (2003). Spectroscopic and Thermochemical Information on the O2−O2 Collisional Complex Inferred From Atmospheric Uv/Visible O4 Absorption Band Profile Measurements. In: Camy-Peyret, C., Vigasin, A.A. (eds) Weakly Interacting Molecular Pairs: Unconventional Absorbers of Radiation in the Atmosphere. NATO Science Series, vol 27. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0025-3_24

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  • DOI: https://doi.org/10.1007/978-94-010-0025-3_24

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-1-4020-1596-0

  • Online ISBN: 978-94-010-0025-3

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