Roaming dynamics in acetone dissociation

DC slice imaging has been employed to study the photodissociation dynamics of acetone at 230 nm, with detection of the CO photoproduct via the B (v' = 0) (1)Sigma(+) <- X (v '' = 0) 121 transition. A bimodal translational energy distribution observed in the CO fragments points to two distinct dissociation pathways in the 230 nm photolysis of acetone. One pathway results in substantial translational energy release (E-ave approximate to 0.3 eV) along with rather high rotational excitation (up to J '' = 50) of CO, and is attributed to the thoroughly investigated stepwise mechanism of bond cleavage in acetone. The other dissociation pathway leads to rotationally cold CO (J" = 0-20) with very little energy partitioned into translation (E-ave approximate to 0.04 eV) and in this way it is dynamically similar to the recently reported roaming mechanism found in formaldehyde and acetaldehyde dissociation. We ascribe the second dissociation pathway to an analogous roaming dissociation mechanism taking place on the ground electronic state following internal conversion. For acetone, this would imply highly vibrationally excited ethane as a coproduct of rotationally cold CO, with the ethane formed above the threshold for secondary decomposition. We estimate that about 15% of the total CO fragments are produced through the roaming pathway. Rotational populations were obtained using a new Doppler-free method that simply relies on externally masking the phosphor screen under velocity map conditions in such a way that only the products with no velocity component along the laser propagation direction are detected.