The specific ion effects are observed ubiquitously throughout chemistry and biology. A number of factors are believed to be at work, some of which include ion size, charge, and polarizability. Free energy calculations have been used to probe the extent of the influence of each of these effects in solution as a stepping stone to even more complex problems. Recent statistical mechanical formulas, derived from physically-motivated partitioning of the free energy, have been applied to compute ion hydration free energies in small droplets of water simulated via classical mechanics. These formulas reduce free energies to a series of ion-water binding energy probability distributions and open up the possibility for sampling a subset of these energies via quantum chemical supermolecular and/or perturbation theory approaches. The results discussed herein offer significant insights into the ion hydration problem, especially when including the air-vapor interface.

Partitioning ion hydration free energies to incorporate quantum chemical sampling

246th National Meeting (2013)

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