The collisions between two oxygen molecules give rise to O4 absorption in the Earth atmosphere. O4 absorption is relevant to atmospheric transmission and Earth’s radiation budget. O4 is further used as a reference gas in Differential Optical Absorption Spectroscopy (DOAS) applications to infer properties of clouds and aerosols. The O4 absorption cross section spectrum of bands centered at 343, 360, 380, 446, 477, 532, 577 and 630 nm is investigated in dry air and oxygen as a function of temperature (203–295°K), and at 820 mbar pressure. We characterize the temperature dependent O4 line shape and provide high precision O4 absorption cross section reference spectra that are suitable for atmospheric O4 measurements. The peak absorption cross-section is found to increase at lower temperatures due to a corresponding narrowing of the spectral band width, while the integrated cross-section remains constant (within o3%, the uncertainty of our measurements). The enthalpy of formation is determined to be ΔH250 = -0.12±0.12 kJ mol-1, which is essentially zero, and supports previous assignments of O4 as collision induced absorption (CIA). At 203°K, van der Waals complexes (O2-dimer) contribute less than 0.14% to the O4 absorption in air. We conclude that O2-dimer is not observable in the Earth atmosphere, and as a consequence the atmospheric O4 distribution is for all practical means and purposes independent of temperature, and can be predicted with an accuracy of better than 10-3 from knowledge of the oxygen concentration profile.
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The first 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 Physique Mol•culaire et Application/Differential Optical Absorption Spectroscopy) balloon gondola. Seven 04 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 ~40 hPa and temperatures (T) ranging from 203 K to 250 K. For the encountered atmospheric condi- tions, it is found that, (a) the band shapes do not change with T and p and (b) the peak collision pair absorption intensities (c•i) concurrently increase with decreasing T (by about 11% over a AT--50 K). 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 04 absorption cross sections are T-independent, the inferred Tdependence of ozi(T) suggests a thermally averaged enthalpy change < AH > ---(1207+83) J/Mol involved in the formation of O4. Our inferred AH is in reasonable agreement with the orientation and spin averaged 04 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 (186 J/Mol).
