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Optimized atomistic force fields for aqueous solutions of Magnesium and Calcium Chloride: Analysis, achievements and limitations

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  • Methodological Aspects of Coarse Graining
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Abstract

Molecular simulations are an important tool in the study of aqueous salt solutions. To predict the physical properties accurately and reliably, the molecular models must be tailored to reproduce experimental data. In this work, a combination of recent global and local optimization tools is used to derive force fields for MgCl2 (aq) and CaCl2 (aq). The molecular models for the ions are based on a Lennard-Jones (LJ) potential with a superimposed point charge. The LJ parameters are adjusted to reproduce the bulk density and shear viscosity of the different solutions at 1 bar and temperatures of 293.15, 303.15, and 318.15 K. It is shown that the σ-value of chloride consistently has the strongest influence on the system properties. The optimized force field for MgCl2 (aq) provides both properties in good agreement with the experimental data over a wide range of salt concentrations. For CaCl2 (aq), a compromise was made between the bulk density and shear viscosity, since reproducing the two properties requires two different choices of the LJ parameters. This is demonstrated by studying metamodels of the simulated data, which are generated to visualize the correlation between the parameters and observables by using projection plots. Consequently, in order to derive a transferable force field, an error of ∼3% on the bulk density has to be tolerated to yield the shear viscosity in satisfactory agreement with experimental data.

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Authors and Affiliations

  1. Fraunhofer-Institute for Algorithms and Scientific Computing, Department of Virtual Material Design, Sankt Augustin, Germany

    Roman Elfgen, Marco Hülsmann, Thorsten Köddermann & Dirk Reith

  2. Bonn-Rhein-Sieg University of Applied Sciences, Department of Mechanical Engineering, Sankt Augustin, Germany

    Marco Hülsmann, Andreas Krämer, Karl N. Kirschner & Dirk Reith

  3. University of Bonn, Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Bonn, Germany

    Roman Elfgen

Authors
  1. Roman Elfgen
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  2. Marco Hülsmann
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  3. Andreas Krämer
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  4. Thorsten Köddermann
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  5. Karl N. Kirschner
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  6. Dirk Reith
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Correspondence to Marco Hülsmann.

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Elfgen, R., Hülsmann, M., Krämer, A. et al. Optimized atomistic force fields for aqueous solutions of Magnesium and Calcium Chloride: Analysis, achievements and limitations. Eur. Phys. J. Spec. Top. 225, 1391–1409 (2016). https://doi.org/10.1140/epjst/e2016-60112-7

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  • DOI: https://doi.org/10.1140/epjst/e2016-60112-7

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