State-resolved imaging of CO from propenal photodissociation: Signatures of concerted three-body dissociation

Abstract

State-selected DC sliced images of propenal photodissociation show clear signatures of a novel synchronous concerted three-body dissociation of propenal recently proposed by Lee and co-workers to give C2H2 + H2 + CO [S. H. Lee, C. H. Chin, C. Chaudhuri, ChemPhysChem 12, 753 (2011)]. Unlike any prior example of a concerted 3-body dissociation event, this mechanism involves breaking three distinct bonds and yields 3 distinct molecules. DC sliced images of CO fragments were recorded for a range of rotational levels for both v = 0 and v = 1. The results show formation of two distinct CO product channels having dissimilar translational energy distributions with characteristic rovibrational state distributions. The images for CO (v = 0) show a large contribution of slower CO fragments at lower rotational levels (J = 5–25). This slow component is completely absent from the v = 1 CO images. The images for the higher rotational levels of the v = 0 and v = 1 CO are nearly identical, and this provides a basis for decomposing the two channels for v = 0. The quantum state and translational energy distributions for the slow channel are readily assigned to the 3-body dissociation based on the properties of the transition state. The faster CO fragments dominating the higher rotational levels in both v = 0 and v = 1 are attributed to formation of CH3CH + CO, also in agreement with the inferences based on previous non-state-resolved measurements with supporting theoretical calculations.