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<front>
<journal-meta>
<journal-id journal-id-type="publisher">ACPD</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics Discussions</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACPD</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7375</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-6-981-2006</article-id>
<title-group>
<article-title>The potential impact of ClO&lt;sub&gt;x&lt;/sub&gt; radical complexes on polar stratospheric ozone loss processes</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Vogel</surname>
<given-names>B.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Feng</surname>
<given-names>W.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Streibel</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Müller</surname>
<given-names>R.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Research Centre J&amp;uuml;lich, Institute for Stratospheric Research (ICG-I), J&amp;uuml;lich, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>School of Earth and Environment, University of Leeds, Leeds, UK</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Alfred Wegener Institute for Polar and Marine Research (AWI), Potsdam, Germany</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>European Ozone Research Coordinating Unit, University of Cambridge, Cambridge, UK</addr-line>
</aff>
<pub-date pub-type="epub">
<day>03</day>
<month>02</month>
<year>2006</year>
</pub-date>
<volume>6</volume>
<issue>1</issue>
<fpage>981</fpage>
<lpage>1022</lpage>
<permissions>
<license xlink:type="simple">
<license-p>This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.</license-p>
</license>
</permissions>
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<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/6/981/2006/acpd-6-981-2006.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/6/981/2006/acpd-6-981-2006.pdf</self-uri>
<abstract>
<p>The importance of radical-molecule complexes for atmospheric chemistry
has been discussed in recent years. In particular, the existence of a
ClO&amp;middot;O&lt;sub&gt;2&lt;/sub&gt; and ClO&lt;sub&gt;x&lt;/sub&gt; water radical complexes like ClO&amp;middot;H&lt;sub&gt;2&lt;/sub&gt;O, OClO&amp;middot;H&lt;sub&gt;2&lt;/sub&gt;O,
OClO&amp;middot;(H&lt;sub&gt;2&lt;/sub&gt;O)&lt;sub&gt;2&lt;/sub&gt;, and ClOO&amp;middot;H&lt;sub&gt;2&lt;/sub&gt;O could play a role in enhancing the ClO
dimer (Cl&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;) formation and therefore may constitute an important
intermediate in polar stratospheric ozone loss cycles. Model
simulations performed with the Chemical Lagrangian Model of the
Stratosphere (CLaMS) will be presented to study the role of radical
complexes on polar stratospheric ozone loss processes. The model
simulations are performed for the Arctic winter 2002/2003 at a level
of 500 K potential temperature and the results are compared to
observed ozone loss rates determined by the Match technique. Moreover,
recently reported values for the equilibrium constant of the ClO
dimer formation are used to restrict the number of possible model
results caused by large uncertainties about radical complex chemistry.
Our model simulations show that the potential impact of ClO&amp;middot;O&lt;sub&gt;2&lt;/sub&gt; on
polar ozone loss processes is small (dO&lt;sub&gt;3&lt;/sub&gt;/dt&amp;#x226A;0.5 ppb/sunlight h)
provided that the ClO&amp;middot;O&lt;sub&gt;2&lt;/sub&gt; complex is only weakly
stable. Assuming that the binding energies of the ClO&lt;sub&gt;x&lt;/sub&gt; water
complexes are much higher than theoretically predicted an enhancement
of the ozone loss rate by up to &amp;asymp;0.5 ppb/sunlight h is
simulated. Because it is unlikely that the ClO&lt;sub&gt;x&lt;/sub&gt; water complexes are
much more stable than predicted we conclude that these complexes have
no impact on polar stratospheric ozone loss processes. Although  large
uncertainties about radical complex chemistry exist, our findings show
that the potential impact of ClO&lt;sub&gt;x&lt;/sub&gt; radical molecule complexes on
polar stratospheric ozone loss processes is very small considering
pure gas-phase chemistry. However the existence of ClO&lt;sub&gt;x&lt;/sub&gt;
radical-molecule complexes could possibly explain discrepancies for
the equilibrium constant of the ClO dimer formation found between
recent laboratory and stratospheric measurements.</p>
</abstract>
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