Solvation Energy of Ions in a Stockmayer Fluid

CJ Shock and MJ Stevens and AL Frischknecht and I Nakamura, JOURNAL OF PHYSICAL CHEMISTRY B, 124, 4598-4604 (2020).

DOI: 10.1021/acs.jpcb.0c00769

We calculate the solvation energy of monovalent and divalent ions in various liquids with coarse-grained molecular dynamics simulations. Our theory treats the solvent as a Stockmayer fluid, which accounts for the intrinsic dipole moment of molecules and the rotational dynamics of the dipoles. Despite the simplicity of the model, we obtain qualitative agreement between the simulations and experimental data for the free energy and enthalpy of ion solvation, which indicates that the primary contribution to the solvation energy arises mainly from the first and possibly second solvation shells near the ions. Our results suggest that a Stockmayer fluid can serve as a reference model that enables direct comparison between theory and experiment and may be invoked to scale up electrostatic interactions from the atomic to the molecular length scale.

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