Two roaming pathways in the photolysis of CH 3 CHO between 328 and 308 nm

The correlated speed and rotational energy distributions of the CO fragment from photodissociation of CH 3 CHO have been measured at a range of wavelengths from 308 to 328 nm. The distributions are bimodal, showing low J , slow speed, and high J , fast speed components. The cold component disappears for λ > 325 nm. This threshold corresponds to C–H bond cleavage and we assign these CO products as arising from roaming of a H-atom about a CH 3 CO core. We attribute the hot component to CO formed through CH 3 -roaming. No evidence was observed for the presence of a transition state mechanism. This is the first time two distinct roaming channels have been observed from the same electronic state. The results support the growing understanding that roaming can be significant in chemical reactions and outweigh traditional pathways.