Time-Resolved Pair-Correlated Imaging of the Photodissociation of Acetaldehyde at 267 nm: Pathway Partitioning.

Photodissociation of acetaldehyde (CH3CHO) by UV excitation involves interwoven multiple reaction pathways, including nonradiative decay, isomerization, transition-state pathway, roaming, and other dissociation mechanisms. Recently, we employed picosecond time-resolved, pair-correlated product imaging in a study of acetaldehyde photodissociation at 267 nm to disentangle those competing mechanisms and to elucidate the possible roaming pathways (Yang, C. H.; Chem. Sci. 2020, 11, 6423-6430). Here, we complement the pair-correlated product speed distribution of CO(v = 0) at the high-j side of the CO rotational state distribution in the CO + CH4 channel and detail the two-dimensional data analysis of the time-resolved images. As a result, extensive comparisons with other studies can be made and the branching fractions of the previously assigned TScc(S0), non-TScc(S0), and CI(S1/S0) pathways for the CO(v = 0) + CH4 molecular channel are evaluated to be 0.74 ± 0.08, 0.15 ± 0.02, and 0.11 ± 0.02, respectively. Together with the macroscopic branching ratio between the molecular (CO + CH4) and radical (CH3 + HCO) channels at 267 nm from the literature, a global view of the microscopic pathways can then be delineated, which provides invaluable insights and should pave the way for further studies of this interesting system.