Effects of solvation shells and cluster size on the reaction of aluminum clusters with water

Reaction of aluminum clusters, Aln (n = 16, 17 and 18), with liquid water is investigated using quantum molecular dynamics simulations, which show rapid production of hydrogen molecules assisted by proton transfer along a chain of hydrogen bonds (H-bonds) between water molecules, i.e. Grotthuss mechanism. The simulation results provide answers to two unsolved questions: (1) What is the role of a solvation shell formed by non-reacting H-bonds surrounding the H-bond chain; and (2) whether the high size-selectivity observed in gas-phase Aln-water reaction persists in liquid phase? First, the solvation shell is found to play a crucial role in facilitating proton transfer and hence H2 production. Namely, it greatly modifies the energy barrier, generally to much lower values (< 0.1 eV). Second, we find that H2 production by Aln in liquid water does not depend strongly on the cluster size, in contrast to the existence of magic numbers in gas-phase reaction. This paper elucidates atomistic mechanisms underlying these observations.