Delayed ionization and fragmentation en route to thermionic emission: Statistics and dynamics

Thermionic emission is discussed as a long time (microseconds) decay mode of energy-rich large molecules, metallic and metcar clusters, and fullerenes. We review what is known and consider the many experiments, systems, and theoretical and computational studies that still need to be done. We conclude with a wish list for future work. Particular attention is given to the experimental signatures, such as the dependence on the mode of energy acquisition, and theoretical indications of a not-quite-statistical delayed ionization and to the competition of electron emission with other decay modes, such as fragmentation or radiative cooling. Coupling of the electronic and nuclear modes can be a bottleneck and quite long time-delayed ionization can be observed, as in the decay of high Rydberg states probed by ZEKE spectroscopy, before the onset of complete energy partitioning.