Absolute hydration free energy of the proton from first-principles electronic structure calculations

Chang Guo Zhan, David A. Dixon

Research output: Contribution to journalArticlepeer-review

264 Scopus citations

Abstract

The absolute hydration free energy of the proton, ΔGhyd298(H+), is one of the fundamental quantities for the thermodynamics of aqueous systems. Its exact value remains unknown despite extensive experimental and computational efforts. We report a first-principles determination of ΔGhyd298(H+) by using the latest developments in electronic structure theory including solvation effects. High level ab initio calculations have been performed with a supermolecule-continuum approach based on a recently developed self-consistent reaction field model known as surface and volume polarization for electrostatic interaction (SVPE) or fully polarizable continuum model (FPCM). In the supermolecule-continuum approach, part of the solvent surrounding the solute is treated quantum mechanically and the remaining bulk solvent is approximated by a dielectric continuum medium. With this approach, the calculated results can systematically be improved by increasing the number of quantum mechanically treated solvent molecules. ΔGhyd298(H+) is accurately predicted to be -262.4 kcal/mol based on high-level, first-principles solvation-included electronic structure calculations. The absolute hydration free energies of other ions can be obtained by using appropriate available thermodynamic data in combination with this value. The high accuracy of the predicted absolute hydration free energy of proton is confirmed by applying the same protocol to predict ΔGhyd298(Li+).

Original languageEnglish
Pages (from-to)11534-11540
Number of pages7
JournalJournal of Physical Chemistry A
Volume105
Issue number51
DOIs
StatePublished - Dec 27 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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