Revised many-body potential energy function for the description of the H3O+(H2O)n clusters

A revised potential energy function that has been fitted to the latest set of Kebarle and coworkers [1982, J. Am. chem. Soc., 104, 1462] entropy and enthalpy measurements at T = 300 K is presented. The model assumes a rigid hydronium unit and accounts for all orders of many-body interactions explicitly. The difference with the older function that had been based on earlier measurements by Kebarle and co-workers [1972, J. Am. chem. Soc., 94, 7627; 1967, J. Am. chem. Soc., 89, 6393] is that more compact clusters are generated. We have studied the structural properties of water clusters in the size range 5-80 at T = 250 K within the framework of the (mu PT) Grand Canonical ensemble. Clusters with sizes less than about 10 water molecules consist of a four-coordinated first shell, where the fourth water molecule is hydrogen bonded to the oxygen atom of the hydronium ion. The hydration number goes through a minimum value similar to 1.6, for a cluster size around 50, and it starts increasing again with further cluster growth, to similar to 2.5 for a cluster size of 250 water molecules, which is the largest cluster examined. On the other hand the water molecule coordination number shows a monotonic increase with cluster size. In small clusters, less than 10, water molecules prefer to be arranged in a chain-like fashion; at sizes around 50, tri-coordinated clathrate-like structures dominate whereas with further size increase the coordination number eventually levels off to the experimental bulk value, at 4.6.