Nonadiabatic Molecular Dynamics of Water Cluster Dissociation by Vacuum Ultraviolet Absorption or Electron Impact Excitation.

Abstract

After five decades of investigation since the 1970s, the nature of photon-induced or electron-induced water dissociation is still largely studied only in the gas phase, with a notable absence of dynamics studies of water clusters and bulk water. We study the problem with density functional theory and the nonadiabatic fewest switches surface hopping technique considering both singlet and triplet excited states to study the dissociation of water clusters leading mainly to OH + H. For clusters of 40 water molecules, the mean dissociation time was found to be <10 fs, and the threshold energy was ∼6 eV. Dissociation is almost exclusively associated with the cluster surface due to the lower energy of surface water excited states relative to the bulk. Recombination plays a major role in vacuum ultraviolet dissociation. O + H2 is found as a minor product in the dissociation and is mostly produced in "roaming" trajectories.