Comparison of fixed charge and polarizable models for predicting the structural, thermodynamic, and transport properties of molten alkali chlorides

HM Wang and RS DeFever and Y Zhang and F Wu and S Roy and VS Bryantsev and CJ Margulis and EJ Maginn, JOURNAL OF CHEMICAL PHYSICS, 153, 214502 (2020).

DOI: 10.1063/5.0023225

Results from extensive molecular dynamics simulations of molten LiCl, NaCl, KCl, and RbCl over a wide range of temperatures are reported. Comparison is made between the "Polarizable Ion Model" (PIM) and the non-polarizable "Rigid Ion Model" (RIM). Densities, self-diffusivities, shear viscosities, ionic conductivities, and thermal conductivities are computed and compared with experimental data. In addition, radial distribution functions are computed from ab initio molecular dynamics simulations and compared with the two sets of classical simulations as well as experimental data. The two classical models perform reasonably well at capturing structural and dynamic properties of the four molten alkali chlorides, both qualitatively and often quantitatively. With the singular exception of liquid density, for which the PIM is more accurate than the RIM, there are few clear trends to suggest that one model is more accurate than the other for the four alkali halide systems studied here.

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