Examination of the structural properties of the H3O+(H2O)n clusters in the (μPT) Grand Canonical ensemble, by employing a new many-body potential-energy function

In the current work we examine the structural properties of water clusters that result from the hydration of a rigid H3O+ ion, under thermal conditions at T=250 K and for four different vapor pressures at 0.0156, 0.0625, 0.25, and 1 mbar. For this purpose we have constructed a model potential function that accounts explicitly not only for the three-body but for all orders of many-body interactions between the ion and the water molecules and for charge transfer effects as well. The adjustable parameters of the potential have been derived within ∼0.1kBT accuracy through a concurrent fit to experimental enthalpy and entropy values from the corresponding cluster growth reactions. Many-body interactions have been found to comprise ∼10% the three-body interactions, a fact that can not be ignored. The calculations have been carried out in the Grand Canonical ensemble (μPT) where cluster sizes with a mean number of 6.69, 9.67, 29.17, and 44.37 water molecules for the four respective vapor pressures, have been gen...

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