Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 17, Issue 48, Pages 32539-32546Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp04977f
Keywords
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Funding
- Academy of Finland
- University of Helsinki
- Israel Science Foundation [172/12]
- National Science Foundation [CHE-090-9227]
- University of California, Irvine's Undergraduate Research Opportunities Program
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Carbonyl oxides, or Criegee intermediates, are formed from the gas phase ozonolysis of alkenes and play a pivotal role in night-time and urban area atmospheric chemistry. Significant discrepancies exist among measurements of the strong (B) over tilde (1)A'-(X) over tilde (1)A' electronic transition of the simplest Criegee intermediate, CH2OO in the visible/near-UV. We report room temperature spectra of the (B) over tilde (1)A'-(X) over tilde (1)A' electronic absorption band of CH2OO acquired at higher resolution using both single-pass broadband absorption and cavity ring-down spectroscopy. The new absorption spectra confirm the vibrational structure on the red edge of the band that is absent from ionization depletion measurements. The absolute absorption cross sections over the 362-470 nm range are in good agreement with those reported by Ting et al. Broad-band absorption spectra recorded over the temperature range of 276-357 K were identical within their mutual uncertainties, confirming that the vibrational structure is not due to hot bands.
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