Strong and selective isotope effect in the vacuum ultraviolet photodissociation branching ratios of carbon monoxide

Rare isotope ((13)C, (17)O and (18)O) substitutions can substantially change absorption line positions, oscillator strengths and photodissociation rates of carbon monoxide (CO) in the vacuum ultraviolet (VUV) region, which has been well accounted for in recent photochemical models for understanding the large isotopic fractionation effects that are apparent in carbon and oxygen in the solar system and molecular clouds. Here, we demonstrate a strong isotope effect associated with the VUV photodissociation of CO by measuring the branching ratios of (12)C(16)O and (13)C(16)O in the Rydberg 4p(2), 5p(0) and 5s(0) complex region. The measurements show that the quantum yields of electronically excited C atoms in the photodissociation of (13)C(16)O are dramatically different from those of (12)C(16)O, revealing strong isotope effect. This isotope effect strongly depends on specific quantum states of CO being excited, which implies that such effect must be considered in the photochemical models on a state by state basis.