Photochemistry. Evidence for direct molecular oxygen production in CO₂ photodissociation

Photodissociation of carbon dioxide (CO2) has long been assumed to proceed exclusively to carbon monoxide (CO) and oxygen atom (O) primary products. However, recent theoretical calculations suggested that an exit channel to produce C + O2 should also be energetically accessible. Here we report the direct experimental evidence for the C + O2 channel in CO2 photodissociation near the energetic threshold of the C((3)P) + O2(X(3)Σ(g)(-)) channel with a yield of 5 ± 2% using vacuum ultraviolet laser pump-probe spectroscopy and velocity-map imaging detection of the C((3)PJ) product between 101.5 and 107.2 nanometers. Our results may have implications for nonbiological oxygen production in CO2-heavy atmospheres.