UV Absorption Cross Sections of ClOOCl Are Consistent with Ozone Degradation Models

@article{Chen2009UVAC,
  title={UV Absorption Cross Sections of ClOOCl Are Consistent with Ozone Degradation Models},
  author={Hsueh-Ying Chen and Chien-Yu Lien and Wei-Yen Lin and Yuan‐Pern Lee and Jim Jr‐Min Lin},
  journal={Science},
  year={2009},
  volume={324},
  pages={781 - 784}
}
Cl in the Sunlight A major assumption in the long-standing mechanistic model for halogen-induced degradation of stratospheric ozone is the steady generation of Cl atoms by photolysis of molecules such as ClOOCl by sunlight. Recently, however, laboratory data raised uncertainties in the ClOOCl absorption cross sections underlying this assumption. Chen et al. (p. 781) undertook precise mass-sensitive cross-section measurements to explore the discrepancy. Molecules were directly quantified before… 
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References

SHOWING 1-10 OF 31 REFERENCES
The UV/Vis absorption spectrum of matrix-isolated dichlorine peroxide, ClOOCl.
TLDR
The results suggest the existence of a ClOOCl electronic state manifold leading to an absorption band similar to those of the near UV spectrum of Cl(2), which could account for the observed ozone depletion in the spring polar stratosphere.
UV Photolysis of ClOOCl
ClOOCl (ClO dimer) photolysis is believed to dominate the catalytic destruction of polar stratospheric ozone during springtime through the production of atomic chlorine. Decomposition by an alternate
Observation of a Heterogeneous Source of OClO from the Reaction of ClO Radicals on Ice
Experiments presented in this contribution demonstrate a heterogeneous source of several chlorine oxides, in particular OClO and ClClO2, from ClO radicals passed over water−ice surfaces at low
Absorption cross sections of the ClO dimer
K. J. Huder and W. B. DeMore*Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109Received: January 10, 1995; In Final Form: February 3, 1995_NASA-CR-200336The
Kinetics of the ClO Self-Reaction and 210 nm Absorption Cross Section of the ClO Dimer
The kinetics of the dimerization of ClO radicals, ClO + ClO + M → Cl2O2 + M (1a), and the 210 nm absorption cross sections of the ClO dimer have been studied using the technique of flash photolysis
First measurements of ClOOCl in the stratosphere: The coupling of ClOOCl and ClO in the Arctic polar vortex
[1] The first measurements of ClOOCl in the stratosphere have been acquired from a NASA ER-2 aircraft, deployed from Kiruna, Sweden (68°N, 21°E), during the joint SOLVE/THESEO-2000 mission of the
Thermal decomposition of ClOOCl.
TLDR
The decomposition rate constants of ClOOCl were directly measured for the first time, and they are higher, depending on temperature and pressure, by factors between 1.5 and 4.2 as compared to experimental data on k-1 by Nickolaisen et al.
The stability and photochemistry of dimers of the ClO radical and implications for Antarctic ozone depletion
Measurements of the ultraviolet spectrum of the Cl2O2 molecule formed at temperatures in the range 203–300 K by recombination of ClO radicals are reported. The equilibrium constant for the reaction
Bond strength of chlorine peroxide.
TLDR
An approximation for the equilibrium constant in the stratospheric temperature regime between 190 and 230 K of the form K(eq) = 1.92 x 10(-27) cm3 molecules(-1) x exp(8430 K/T) is provided, lower than current reference data and agrees well with high altitude aircraft measurements within their scattering range.
Large losses of total ozone in Antarctica reveal seasonal ClOx/NOx interaction
Recent attempts1,2 to consolidate assessments of the effect of human activities on stratospheric ozone (O3) using one-dimensional models for 30° N have suggested that perturbations of total O3 will
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