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

• Published in: Atmospheric Chemistry and Physics
• Main Authors: C. M. Roehl, Z. Marka, J. L. Fry, P. O. Wennberg
• Format: Article
• Language: English
• Published: Copernicus Publications 2007-01-01
• Online Access: http://www.atmos-chem-phys.net/7/713/2007/acp-7-713-2007.pdf

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.