Maxwell-Boltzmann versus non-ergodic events in the velocity distribution of water molecules evaporated from protonated water nanodroplets

Measurement of velocity distributions of evaporated water monomers from small mass- and energy-selected protonated water clusters allows probing the extent of thermalization after excitation of these ultimately small nanodroplets. Electronic excitation of a molecule in the cluster is here induced by a single collision with an argon atom in the keV energy range. The measured velocity distributions of the departing neutral molecules exhibit bimodal shapes with a lower-velocity part consistent with a complete redistribution of the deposited energy in the entire cluster and a higher-velocity contribution corresponding to evaporation before complete energy redistribution. Statistical molecular dynamics calculations reproduce the bimodal shape of the velocity distributions by assuming an initial spreading of the excitation energy among all modes, thereby reproducing the lower velocity contribution of the distribution. By contrast, assuming the deposited energy to be initially localized among the modes of a sing...