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The H2O-O2 water vapour complex in the Earth's atmosphere

by Y. Kasai, E. Dupuy, R. Saito, K. Hashimoto, A. Sabu, S. Kondo, Y. Sumiyoshi, Y. Endo
Atmospheric Chemistry and Physics ()
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Until recently, abundance estimates for bound molecular complexes have\nbeen affected by uncertainties of a factor 10-100. This is due to the\ndifficulty of accurately obtaining the equilibrium constant, either from\nlaboratory experiments or by statistical thermodynamic calculations. In\nthis paper, we firstly present laboratory experiments that we performed\nin order to determine the molecular structure of H(2)O-O(2). We also\nderive global abundance estimates for H(2)O-O(2) in the Earth's\natmosphere. The equilibrium constant K(p) evaluated using the\n``anharmonic oscillator approach{''} (AHOA) (Sabu et al., 2005) was\nemployed: the AHOA explains well the structure of the complex obtained\nby the present experiment. The K(p) calculated by this method shows a\nrealistic temperature dependence. We used this K(p) to derive global\nabundance estimates for H(2)O-O(2) in the Earth's atmosphere. The\ndistribution of H(2)O-O(2) follows that of water vapour in the\ntroposphere and seems inversely proportional to temperature in the lower\nstratosphere. Preliminary estimates at the surface show amount of\nH(2)O-O(2) is comparable to CO or N(2)O, ranking water vapour complexes\namong the ten most abundant species in the boundary layer.

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