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@ARTICLE{vonHobe:57412,
author = {von Hobe, M. and Salawitch, R. J. and Canty, T. and
Keller-Rudek, H. and Moortgat, G. K. and Grooß, J.-U. and
Müller, R. and Stroh, F.},
title = {{U}nderstanding the kinetics of the {CIO} dimer cycle},
journal = {Atmospheric chemistry and physics},
volume = {7},
issn = {1680-7316},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {PreJuSER-57412},
pages = {3055 - 3069},
year = {2007},
note = {Record converted from VDB: 12.11.2012},
abstract = {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.},
keywords = {J (WoSType)},
cin = {ICG-1},
ddc = {550},
cid = {I:(DE-Juel1)VDB790},
pnm = {Atmosphäre und Klima},
pid = {G:(DE-Juel1)FUEK406},
shelfmark = {Meteorology $\&$ Atmospheric Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000247572500001},
doi = {10.5194/acp-7-3055-2007},
url = {https://juser.fz-juelich.de/record/57412},
}