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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
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Volume 7, issue 3
Atmos. Chem. Phys., 7, 713–720, 2007
https://doi.org/10.5194/acp-7-713-2007
© Author(s) 2007. This work is licensed under
the Creative Commons Attribution-NonCommercial-ShareAlike 2.5 License.
Atmos. Chem. Phys., 7, 713–720, 2007
https://doi.org/10.5194/acp-7-713-2007
© Author(s) 2007. This work is licensed under
the Creative Commons Attribution-NonCommercial-ShareAlike 2.5 License.

  14 Feb 2007

14 Feb 2007

Near-UV photolysis cross sections of CH3OOH and HOCH2OOH determined via action spectroscopy

C. M. Roehl1, Z. Marka1,*, J. L. Fry2,**, and P. O. Wennberg1,3 C. M. Roehl et al.
  • 1Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA
  • 2Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA
  • 3Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA 91125, USA
  • *now at: Columbia Astrophysics Laboratory, Columbia University, New York, NY 10027, USA
  • **now at: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720-1460, USA

Abstract. Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.

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