Primary Product Branching in the Photodissociation of Chloroacetaldehyde at 157 nm

We used crossed laser-molecular beam scattering to study the primary photodissociation channels of chloroacetaldehyde (CH₂ClCHO) at 157 nm. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence two other photodissociation channels: HCl photoelimination and C-C bond fission. This is the first direct evidence of the C-C bond fission channel in chloroacetaldehyde, and we found that it significantly competes with the C-Cl bond fission channel. We determined the total primary photodissociation branching fractions for C-Cl fission:HCl elimination:C-C fission to be 0.65:0.07:0.28. The branching between the primary channels suggests the presence of interesting excited state dynamics in chloroacetaldehyde. Some of the vinoxy radicals from C-Cl photofission and most of the ketene cofragments formed in HCl photoelimination have enough internal energy to undergo secondary dissociation. While our previous velocity map imaging study on the photodissociation of chloroacetaldehyde at 157 nm focused on the barrier for the unimolecular dissociation of vinoxy to H + ketene, this work shows that the HCl elimination channel contributed to the high kinetic energy portion of the m/z = 42 signal in that study.