The single-photon ionization mass spectrometry of primary photofragments of chlorine monoxide (ClO) is reported. The use of laser-produced plasma (LPP) radiation in pump–probe experiments allows us to ionize the laser-generated atomic photoproducts with tunable radiation in the vacuum ultraviolet regime (E = 10–18 eV). Autoionization resonances of the atomic photoproducts are used to establish the quantum states of the photoproducts and to enhance the detection sensitivity. Predissociation and direct dissociation of A (2Π)-excited ClO yields Cl (2 P )+ O (3 P ) as well as Cl (2 P )+ O (1 D ), respectively. The quantum yield of O (1 D ) formation is reported in the threshold regime near the ClO [ A (2Π)] dissociation limit.
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