Photofragment Imaging of Carbon Cluster Cations: Explosive Ring Rupture

Carbon cluster cations (C⁺) produced by laser vaporization are mass selected and photodissociated at 355 nm. Multiphoton dissociation of smaller ions leads to the elimination of neutral C₃, as in previous work, whereas larger clusters exhibit more varied fragmentation channels. Photofragment velocity-map imaging detects significant kinetic energy release (KER) in the various n - 3 cation fragments. Small cations (n = 6 or 7) with linear structures produce moderate KER, whereas larger cations (n = 10, 11, 12, 15, or 20) having monocyclic ring structures produce much higher KER values. Such high KER values are unanticipated, as optical excitation should produce a wide distribution of internal energies. These carbon clusters have a surprising ability to absorb multiple photons of ultraviolet radiation, achieving a state of extreme excitation prior to dissociation. The remarkable nonstatistical distribution of energy is apparently influenced by the significant ring strain that can be released upon photodissociation.