Absolute hydration free energy scale for alkali and halide ions established from simulations with a polarizable force field

J Phys Chem B. 2006 Feb 23;110(7):3308-22. doi: 10.1021/jp056043p.

Abstract

A polarizable potential function for the hydration of alkali and halide ions is developed on the basis of the recent SWM4-DP water model [Lamoureux, G.; MacKerell, A. D., Jr.; Roux, B. J. Chem. Phys. 2003, 119, 5185]. Induced polarization is incorporated using classical Drude oscillators that are treated as auxiliary dynamical degrees of freedom. The ions are represented as polarizable Lennard-Jones centers, whose parameters are optimized to reproduce the binding energies of gas-phase monohydrates and the hydration free energies in the bulk liquid. Systematic exploration of the parameters shows that the monohydrate binding energies can be consistent with a unique hydration free energy scale if the computed hydration free energies incorporate the contribution from the air/water interfacial electrostatic potential (-540 mV for SWM4-DP). The final model, which can satisfyingly reproduce both gas and bulk-phase properties, corresponds to an absolute scale in which the intrinsic hydration free energy of the proton is -247 kcal/mol.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Air
  • Anions
  • Cations
  • Chemistry, Physical / methods*
  • Computer Simulation
  • Ions*
  • Models, Molecular
  • Models, Statistical
  • Static Electricity
  • Thermodynamics
  • Water / chemistry

Substances

  • Anions
  • Cations
  • Ions
  • Water