  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.

Statistical Mechanics;Soft Condensed Matter;Chemical Physics