Thermodynamics of Small Alkali Metal Halide Cluster Ions [electronic resource] : Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry
- Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- 488-500 : digital, PDF file
- Additional Creators:
- Oak Ridge National Laboratory
United States. Department of Energy. Office of Basic Energy Sciences
United States. Department of Energy. Office of Scientific and Technical Information
- We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.
- Published through SciTech Connect.
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 119 3 ISSN 1089-5639 AC
Lukas Vlcek; Filip Uhlik; Filip Moucka; Ivo Nezbeda; Ariel A. Chialvo.
- Funding Information:
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