MST continuum study of the hydration free energies of monovalent ionic species

TitleMST continuum study of the hydration free energies of monovalent ionic species
Publication TypeJournal Article
Year of Publication2005
AuthorsCurutchet, C, Bidon-Chanal A, Soteras I, Orozco M, Luque FJ
JournalJournal of Physical Chemistry B
Pagination3565 - 3574
Date Published2005
ISBN Number1520-6106
Keywordsab-initio, anisotropic dielectrics, aqueous-solution, carboxylic-acids, charge-distribution, electronic-structure calculations, electrostatic free-energy, gas-phase acidities, numerical applications, solvation free-energies
AbstractIn this study, we revisit the protocol previously proposed within the framework of the Miertus-Scrocco-Tomasi (MST) continuum model to define the cavity between the solute and solvent for predicting hydration free energies of univalent ions [Orozco, M.; Luque, F. J. Chem. Phys. 1994, 182, 237]. The protocol relies on the use of a reduced cavity (around 10-15% smaller than the cavity used for neutral compounds) around the atom(s) bearing the formal charge. The suitability of this approach is examined here for a series of 47 univalent ions for which accurate experimental hydration free energies are available. Attention is also paid to the effect of the charge renormalization protocol used to correct uncertainties arising from the electron density located outside the solute cavity. The method presented here provides, with a minimum number of fitted parameters, reasonable estimates within the experimental error of the hydration free energy of ions (average relative error of 4.7%) and is able to reproduce solvation in water of both small and large ions.