Photolysis of Nitrogen Dioxide at 3660 and 4047 Å at 25°C

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Abstract
Nitrogen dioxide was irradiated at 3660 and 4047 Å at various pressures of NO2, with and without CO2, NO, and N2 as added gases. The data indicate a primary dissociation at 3660 Å and shorter wavelengths corresponding to energies greater than the ON–O bond energy. At 4047 Å, the data are explained by an excited‐molecule mechanism. Isotopic oxygen scrambling experiments at 4047 Å indicate the probability of reactions to produce oxygen atoms at that wavelength, but photolysis of NO2 at trace concentrations and high inert‐gas pressures indicates that these atoms are not derived from the unimolecular decomposition of the photoactivated molecule. The inhibition of the quantum yield by NO addition was pressure‐dependent, lending further support to the premise that oxygen atoms are important in the mechanism at 4047 Å. It is postulated that the reaction NO2*+NO2→N2O3+O is the source of atomic oxygen.