This study utilized a mass-resolved detection of ClOOCl to determine its photodissociation cross section, which is the product of the absorption cross section and dissociation quantum yield. An effusive molecular beam of ClOOCl was generated and its photodissociation probability was determined through measuring the decrease in the ClOOCl beam intensity upon laser irradiation. By comparing with a reference molecule, the absolute cross sections of ClOOCl were obtained without knowing its absolute concentration. The determined cross section of ClOOCl at 248.4 nm is (8.85+/-0.42)x10(-18) cm(2) at 200 K, significantly larger than previously reported values. The temperature dependence of the cross section was investigated at 248.4 nm in the range of 160-260 K; only a very small and negative temperature effect was observed. Because 248.4 nm is very close to the peak of the UV absorption band of ClOOCl, this work provides a new calibration point for normalizing relative absorption spectra of ClOOCl. In this work, the photodissociation cross section at 266 nm and 200 K was also reported to be (4.13+/-0.21)x10(-18) cm(2).

Recently, discrepancies in laboratory measurements of chlorine peroxide (ClOOCl) absorption cross sections have cast doubt on the validity of current photochemical models for stratospheric ozone degradation. Whereas previous ClOOCl absorption measurements all suffered from uncertainties due to absorption by impurities, we demonstrate here a method that uses mass-selected detection to circumvent such interference. The cross sections of ClOOCl were determined at two critical wavelengths (351 and 308 nanometers). Our results are sufficient to resolve the controversial issue originating from the ClOOCl laboratory cross sections and suggest that the highest laboratory estimates for atmospheric photolysis rates of ClOOCl, which best explain the field measurements via current chemical models, are reasonable.

The photolysis rate of ClOOCl is crucial in the catalytic destruction of polar stratospheric ozone. In this work, we determined the photodissociation cross section of ClOOCl at 330 nm with a molecular beam and with mass-resolved detection. The photodissociation cross section is the product of the absorption cross section and the dissociation quantum yield. We formed an effusive molecular beam of ClOOCl at a nozzle temperature of 200 or 250 K and determined its photodissociation probability by measuring the decrease of the ClOOCl intensity upon laser irradiation. By comparing with a reference molecule (Cl(2)), of which the absorption cross section and dissociation quantum yield are well-known, we determined the absolute photodissociation cross section of ClOOCl at 330 nm to be (2.31 +/- 0.11) x 10(-19) cm(2) at 200 K and (2.47 +/- 0.12) x 10(-19) cm(2) at 250 K. Impurity interference has been a well-recognized problem in conventional spectroscopic studies of ClOOCl; our mass-resolved measurement directly overcomes such a problem. This measurement of the ClOOCl photolysis cross section at 330 nm is particularly useful in constraining its atmospheric photolysis rate, which in the polar stratosphere peaks near this wavelength.