Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton

TLDR

The cluster pair approximation has been employed to estimate the absolute aqueous solvation free energy of the proton, but earlier studies used limited ion datasets. The authors used thermochemical cycles involving pKa, gas‑phase acidities, and clustering free energies with the cluster pair approximation, then expanded their dataset to include 121 unclustered ions and 147 clustered ions with up to six water molecules. They obtained an absolute aqueous solvation free energy of the proton of –265.9 kcal mol⁻¹ with an uncertainty of at least 2 kcal mol⁻¹, agreeing with prior work, and demonstrated that.

Abstract

Thermochemical cycles that involve pKa, gas-phase acidities, aqueous solvation free energies of neutral species, and gas-phase clustering free energies have been used with the cluster pair approximation to determine the absolute aqueous solvation free energy of the proton. The best value obtained in this work is in good agreement with the value reported by Tissandier et al. (Tissandier, M. D.; Cowen, K. A.; Feng, W. Y.; Gundlach, E.; Cohen, M. J.; Earhart, A. D.; Coe, J. V. J. Phys. Chem. A 1998, 102, 7787), who applied the cluster pair approximation to a less diverse and smaller data set of ions. We agree with previous workers who advocated the value of -265.9 kcal/mol for the absolute aqueous solvation free energy of the proton. Considering the uncertainties associated with the experimental gas-phase free energies of ions that are required to use the cluster pair approximation as well as analyses of various subsets of data, we estimate an uncertainty for the absolute aqueous solvation free energy of the proton of no less than 2 kcal/mol. Using a value of -265.9 kcal/mol for the absolute aqueous solvation free energy of the proton, we expand and update our previous compilation of absolute aqueous solvation free energies; this new data set contains conventional and absolute aqueous solvation free energies for 121 unclustered ions (not including the proton) and 147 conventional and absolute aqueous solvation free energies for 51 clustered ions containing from 1 to 6 water molecules. When tested against the same set of ions that was recently used to develop the SM6 continuum solvation model, SM6 retains its previously determined high accuracy; indeed, in most cases the mean unsigned error improves when it is tested against the more accurate reference data.