Gas phase spectra of HOBr and Br2O and their atmospheric significance

Abstract

The HOBr molecule is a potential reservoir of Br compounds in the atmosphere. In this work, the UV-visible spectrum of HOBr was measured over the range 242–400 nm. Its absorption consists of two maxima at 280 nm (σ_max=2.7±0.4×10^–19 cm² molecules^–1) and 355 nm (σ_max=7.0±1.1×10^–20 cm² molecules^–1), respectively, where the error is ±1Σ. Atmospheric photolysis lifetime calculations for HOBr in the lower stratosphere have been made using the PHOTOGT model. The results show a strong dependence on the solar zenith angle (SZA) implying a longer lifetime at high latitudes and a relatively short lifetime at low latitudes for example 714 s (albedo of 25%, SZA of 20^° and an altitude of 17 km), and 3226 s (albedo of 25%, SZA of 88^° and an altitude of 17 km). The UV-visible absorption spectrum of Br₂O, which is an intermediate in the preparation, used in this study and is together with H₂O in equilibrium with HOBr, was measured from 205 to 450 nm. The spectrum shows a maximum at 315 nm (σ_max=2.3±0.3×10^–18 cm² molecules^–1) with a shoulder at 355 nm. From the results of the atmospheric lifetime calculations for Br₂O, it is clear that this molecule has a short stratospheric lifetime and is not likely to have a large daytime concentration, for example, 20 s (albedo of 25%, SZA of 20^° and an altitude of 17 km), and 83 s (albedo and 25%, SZA of 88^° and an altitude of 17 km).