Ab initio molecular dynamics calculations of ion hydration free energies

Abstract

We apply ab initio molecular dynamics (AIMD) methods in conjunction with the thermodynamic integration or "lambda-path" technique to compute the intrinsic hydration free energies of Li+, Cl-, and Ag+ ions. Using the Perdew-Burke-Ernzerhof functional, adapting methods developed for classical force field applications, and with consistent assumptions about surface potential (phi) contributions, we obtain absolute AIMD hydration free energies (Delta G(hyd)) within a few kcal/mol, or better than 4%, of Tissandier 's [J. Phys. Chem. A 102, 7787 (1998)] experimental values augmented with the SPC/E water model phi predictions. The sums of Li+/Cl- and Ag+/Cl- AIMD Delta G(hyd), which are not affected by surface potentials, are within 2.6% and 1.2 % of experimental values, respectively. We also report the free energy changes associated with the transition metal ion redox reaction Ag++Ni+-> Ag+Ni2+ in water. The predictions for this reaction suggest that existing estimates of Delta G(hyd) for unstable radiolysis intermediates such as Ni+ may need to be extensively revised.

18 pages, 8 figures. This version is essentially the one published in J. Chem. Phys

References in corpus (6)

• Towards an assessment of the accuracy of density functional theory for first principles simulations of water II
• Absolute Hydration Free Energies of Ions, Ion-Water Clusters, and Quasi-chemical Theory
• Tuning ion coordination preferences to enable selective permeation
• On "the complete basis set limit" and plane-wave methods in first-principles simulations of water
• Energies of ions in water and nanopores within Density Functional Theory
• Ab initio molecular dynamics study of manganese porphine hydration and interaction with nitric oxide

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