1Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark
2Department of Environmental Science and Technology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan
3Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan
4Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554, Japan
5Max-Planck-Institut für Dynamik und Selbstorganisation, 37073 Göttingen, Germany
Abstract. The isotopic fractionation in OCS photolysis is studied theoretically from first principles. UV absorption cross sections for OCS, OC33S, OC34S, OC36S and O13CS are calculated using the time-depedent quantum mechanical formalism and a recently developed ab-initio description of the photodissociation of OCS which takes into account the lowest four singlet and lowest four triplet electronic states. The calculated isotopic fractionations as a function of wavelength are in good agreement with recent measurements by Hattori et al. (2011) and indicate that photolysis leads to only a small enrichment of 34S in the remaining OCS. The photodissociation dynamics provide strong evidence that the photolysis quantum yield is unity at all wavelengths for atmospheric UV excitation, for all isotopologues. A simple stratospheric model is constructed taking into account the main sink reactions of OCS and it is found that overall stratospheric removal slightly favors light OCS in constrast to the findings of Leung et al. (2002). These results show, based on isotopic considerations, that OCS is an acceptable source of background stratosperic sulfate aerosol in agreement with a recent model study of of Brühl et al. (2012). The 13C isotopic fractionation due to photolysis of OCS in the upper stratosphere is significant and will leave a clear signal in the remaining OCS making it a candidate for tracing using the ACE-FTS and MIPAS data sets.