Ab initio molecular dynamics calculations of ion hydration free energies

Details Ab initio molecular dynamics calculations of ion hydration free energies Ab initio molecular dynamics calculations of ion hydration free energies

2009-06-22

arxiv.org/abs/0906.4077v2

Journal of Chemical Physics 130 (20), 204507 (2009)

Physics

Condensed Matter

Statistical Mechanics

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

Scientific paper

10.1063/1.3137054

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.

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