Ion Solvation Thermodynamics from Simulation with a Polarizable Force Field

Alan Grossfield, Pengyu Ren, Jay W. Ponder

Research output: Contribution to journalArticlepeer-review

433 Scopus citations


Thermodynamic measurements of the solvation of salts and electrolytes are relatively straight-forward, but it is not possible to separate total solvation free energies into distinct cation and anion contributions without reference to an additional extrathermodynamic assumption. The present work attempts to resolve this difficulty using molecular dynamics simulations with the AMOEBA polarizable force field and perturbation techniques to directly compute absolute solvation free energies for potassium, sodium, and chloride ions in liquid water and formamide. Corresponding calculations are also performed with two widely used nonpolarizable force fields. The simulations with the polarizable force field accurately reproduce in vacuo quantum mechanical results, experimental ion-cluster solvation enthalpies, and experimental solvation free energies for whole salts, while the other force fields do not. The results indicate that calculations with a polarizable force field can capture the thermodynamics of ion solvation and that the solvation free energies of the individual ions differ by several kilocalories from commonly cited values.

Original languageEnglish
Pages (from-to)15671-15682
Number of pages12
JournalJournal of the American Chemical Society
Issue number50
StatePublished - Dec 17 2003


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