Abstract
The photodissociation dynamics of OClO(2A2 ν1ν2ν3) → Cl(2PJ) + O2 is investigated in the wavelength region between 360 and 450 nm. Observation of nascent chlorine atom fragments produced in their electronic ground state is performed by means of three-photon excitation with subsequent recording of the vacuum ultraviolet laser-induced fluorescence. Mode-specific branching ratios between the dominant ClO(X2ΠΩ) + O(3PJ) and the minor Cl(2PJ) + O2 channel are obtained. The observed quantum yield for Cl production is determined to be below 3.6% at photolysis wavelengths between 365 and 450 nm depending on the respective vibrational level of OClO(2A2ν1ν2ν3). At dissociation wavelengths below 365 nm, a sharp rise in the chlorine formation is observed resulting from a secondary photolysis step where vibrationally excited ClO(X2ΠΩ, v ≥ 4) radicals are dissociated.
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