The formation of cyclic water complexes by sequential ring insertion: Experiment and theory

摘要

The growth of water clusters in liquid helium droplets results in the formation of cyclic structures up to and including the hexamer. In view of the sequential nature of the molecular pick-up process, the formation of water rings involves the insertion of water monomers into preformed cyclic water clusters. The implication of this observation is that the barriers to the ring insertion process are low enough to be overcome during the experiment. This paper presents a combined experimental and theoretical effort to explore the insertion process in detail. Our results provide important new insights into the dynamics of hydrogen-bonded networks. We map out the cluster potential energy surfaces and visualize them using disconnectivity graphs. Nonequilibrium walks on these surfaces show that ring water clusters can be formed during sequential addition of water molecules by surmounting small barriers that are thermally accessible even at the low temperature of the experiment. We find that the effects of zero-point energy are significant in making these processes feasible.