Mass-analyzed velocity map imaging of doubly charged photofragments from C70

Abstract

The velocity distributions of the fragments produced by dissociative photoionization of C(70) have been measured at several photon energies in the extreme UV region, by using a flight-time resolved velocity map imaging (VMI) technique combined with a high-temperature molecular beam and synchrotron radiation. Average kinetic energy release was estimated for the six reaction steps of consecutive C(2) emission, starting from C(70)(2+) → C(68)(2+) + C(2) to C(60)(2+)→ C(58)(2+) + C(2). The total kinetic energy generated in each step shows a general tendency to increase with increasing hν, except for the first and fifth steps. This propensity reflects statistical redistributions of the excess energy in the transition states for the above fragmentation mechanism. Analysis based on the finite-heat-bath theory predicts the detectable minimum cluster sizes at the end of the C(2)-emission decay chain. They accord well with the minimum sizes of the observed ions, if the excess energy in the primary C(70)(2+) is assumed to be smaller by ~15 eV than the maximum available energy. The present VMI experiments reveal remarkably small kinetic energy release in the fifth step, in contradiction to theoretical predictions, which suggests involvement of other fragmentation mechanisms in the formation of C(60)(2+).