Imaging charge transfer in a cation-π system: velocity-map imaging of Ag(+)(benzene) photodissociation.

Ag(+)(benzene) complexes are generated in the gas phase by laser vaporization and mass selected in a time-of-flight spectrometer. UV laser excitation at either 355 or 266 nm results in dissociative charge transfer (DCT), leading to neutral silver atom and benzene cation products. Kinetic energy release in translationally hot benzene cations is detected using a new instrument designed for photofragment imaging of mass-selected ions. Velocity-map imaging and slice imaging techniques are employed. In addition to the expected translational energy release, DCT of Ag(+)(benzene) produces a distribution of internally hot benzene cations. Compared with experiments at 355 nm, 266 nm excitation produces only slightly higher translational excitation and a much greater fraction of internally hot benzene ions. The maximum kinetic energy release in the photodissociation sets an upper limit on the Ag(+)(benzene) dissociation energy of 32.8 (+1.4/-1.5) kcal/mol.