title: Nitryl chloride (ClNO2): UV/vis absorption spectrum between 210 and 296 K and O(3P) quantum yield at 193 and 248 nm.
abstract: Recent studies have shown that the UV/vis photolysis of nitryl chloride (ClNO2) can be a major source of reactive chlorine in the troposphere. The present work reports measurements of the ClNO2 absorption spectrum and its temperature dependence between 210 and 296 K over the wavelength range 200–475 nm using diode array spectroscopy. The room temperature spectrum obtained in this work was found to be in good agreement with the results from Ganske et al. (J. Geophys. Res. 1992, 97, 7651) over the wavelength range common to both studies (200–370 nm) but differs systematically from the currently recommended spectrum for use in atmospheric models. The present results lead to a decrease in the calculated atmospheric ClNO2 photolysis rate by 30%. Including the temperature dependence of the ClNO2 spectrum decreases the calculated atmospheric photolysis rate at lower temperatures (higher altitudes) even further. A parametrization of the wavelength and temperature dependence of the ClNO2 spectrum is presented. O(3P) quantum yields, Φ(ClNO2)(O), in the photolysis of ClNO2 at 193 and 248 nm were measured at 296 K using pulsed laser photolysis combined with atomic resonance fluorescence detection of O(3P) atoms. Φ(ClNO2)(O)(λ) was found to be 0.67 ± 0.12 and 0.15 ± 0.03 (2σ error limits, including estimated systematic errors) at 193 and 248 nm, respectively, indicating that multiple dissociation channels are active in the photolysis of ClNO2 at these wavelengths. The Φ(ClNO2)(O)(λ) values obtained in this work are discussed in light of previous ClNO2 photodissociation studies and the differences are discussed.
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, Boulder, Colorado 80305, United States.
authors.forename: Buddhadeb
authors.initials: B
authors.lastname: Ghosh
authors.forename: Dimitrios K
authors.initials: DK
authors.lastname: Papanastasiou
authors.forename: Ranajit K
authors.initials: RK
authors.lastname: Talukdar
authors.forename: James M
authors.initials: JM
authors.lastname: Roberts
authors.forename: James B
authors.initials: JB
authors.lastname: Burkholder