Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15

This is the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

The MPI-Mainz UV/VIS spectral atlas of gaseous molecules of atmospheric interest

We present the MPI-Mainz UV/VIS Spectral Atlas of Gaseous Molecules, which is a large collection of absorption cross sections and quantum yields in the ultraviolet and visible (UV/VIS) wavelength region for gaseous molecules and radicals primarily of atmospheric interest. The data files contain results of individual measurements, covering research of almost a whole century. To compare and visualize the data sets, multicoloured graphical representations have been created. The MPI-Mainz UV/VIS Spectral Atlas is available on the Internet at <a href="http://www.uv-vis-spectral-atlas-mainz.org"target="_blank">http://www.uv-vis-spectral-atlas-mainz.org</a>. It now appears with improved browse and search options, based on new database software. In addition to the Web pages, which are continuously updated, a frozen version of the data is available under the <a href="http://dx.doi.org/10.5281/zenodo.6951"target="_blank">doi:10.5281/zenodo.6951</a>

Understanding the kinetics of the ClO-Dimer cycle

International audienceAmong the major factors controlling ozone loss in the polar winter is the kinetics of the ClO dimer catalytic cycle. The most important issues are the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate. All these issues have been addressed in a large number of laboratory, field and theoretical studies, but large discrepancies between individual results exist and a self-consistent set of parameters compatible with field observations of ClO and Cl2O2 has not been identified. Here, we use thermodynamic calculations and unimolecular rate theory to constrain the ClO/Cl2O2 equilibrium constant and the rate constants for Cl2O2 formation and dissociation. This information is used together with available atmospheric data to examine Cl2O2 photolysis rates based on different Cl2O2 absorption cross sections. Good overall consistency is achieved using a ClO/Cl2O2 equilibrium constant recently suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on averaged absorption cross sections that are roughly intermediate between the JPL 2002 assessment and a laboratory study by Burkholder et al. (1990)

Understanding the kinetics of the CIO dimer cycle

Among the major factors controlling ozone loss in the polar vortices in winter/spring is the kinetics of the ClO dimer catalytic cycle. Here, we propose a strategy to test and improve our understanding of these kinetics by comparing and combining information on the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate from laboratory experiments, theoretical studies and field observations. Concordant with a number of earlier studies, we find considerable inconsistencies of some recent laboratory results with rate theory calculations and stratospheric observations of ClO and Cl2O2. The set of parameters for which we find the best overall consistency - namely the ClO/Cl2O2 equilibrium constant suggested by Plenge et al. ( 2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. ( 1994) and Cl2O2 photolysis rates based on absorption cross sections in the range between the JPL 2006 assessment and the laboratory study by Burkholder et al. ( 1990) - is not congruent with the latest recommendations given by the JPL and IUPAC panels and does not represent the laboratory studies currently regarded as the most reliable experimental values. We show that the incorporation of new Pope et al. ( 2007) Cl2O2 absorption cross sections into several models, combined with best estimates for other key parameters ( based on either JPL and IUPAC evaluations or on our study), results in severe model underestimates of observed ClO and observed ozone loss rates. This finding suggests either the existence of an unknown process that drives the partitioning of ClO and Cl2O2, or else some unidentified problem with either the laboratory study or numerous measurements of atmospheric ClO. Our mechanistic understanding of the ClO/Cl2O2 system is grossly lacking, with severe implications for our ability to simulate both present and future polar ozone depletion