Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 130, Issue 20, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3137054
Keywords
ab initio calculations; association; atom-ion reactions; chlorine; free energy; lithium; molecular dynamics method; negative ions; nickel; positive ions; radiolysis; reaction kinetics theory; reduction (chemical); silver; solvation; water
Funding
- National Institutes of Health through the NIH Road Map for Medical Research
- SNL Truman Program LDRD [120209]
- Department of Energy [DE-AC04-94AL85000]
- Sandia Corporation
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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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