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Ab initio molecular dynamics calculations of ion hydration free energies

J. Chem. Phys. 130, 204507 (2009); doi:10.1063/1.3137054

Published 27 May 2009

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Kevin Leung,1 Susan B. Rempe,2 and O. Anatole von Lilienfeld3
1Department of Surface and Interface Sciences, MS 1415, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA
2Department of Nanobiology, MS 0895, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA
3Department of Multiscale Dynamic Materials Modeling, MS 1322, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA
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 (DeltaGhyd) within a few kcal/mol, or better than 4%, of Tissandier et al.'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 DeltaGhyd, 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 DeltaGhyd for unstable radiolysis intermediates such as Ni+ may need to be extensively revised. ©2009 American Institute of Physics
History: Received 12 February 2009; accepted 25 April 2009; published 27 May 2009
Permalink: http://link.aip.org/link/?JCPSA6/130/204507/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Wt
    Computational modeling and simulation of chemical kinetics
  • 82.60.-s
    Chemical thermodynamics
  • 82.30.Fi
    Ion-molecule, ion-ion, and charge-transfer chemical reactions
  • 82.30.Nr
    Association, addition, insertion, cluster formation (chemical reactions)
  • 82.50.-m
    Photochemistry
  • YEAR: 2009

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0021-9606 (print)   1089-7690 (online)
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