Molecular Dynamics Study of Polarizable Ion Models for Molten AgBr

TL;DR

This study compares different polarizable ion models for molten AgBr using molecular dynamics, finding that the PIM1 model best reproduces experimental structural and transport properties, while some models exhibit unphysical behavior.

Contribution

It introduces and evaluates three polarizable ion models for molten AgBr, highlighting the limitations of the PIM2s model and validating the PIM1 model against experimental data.

Findings

PIM1 reproduces neutron diffraction data well.

PIM1's conductivity matches experimental values.

PIM2s exhibits unphysical polarization behavior.

Abstract

Three different polarizable ion models for molten AgBr have been studied by molecular dynamics simulations. The three models are based on a rigid ion model (RIM) with a pair potential of the type proposed by Vashishta and Rahman for alpha-AgI, to which the induced dipole polarization of the ions is added. In the first (PIM1), the dipole moments are only induced by the local electric field; while in the other two (PIM1s and PIM2s), a short-range overlap induced polarization opposes the electrically induced dipole moments. In the PIM1 and the PIM1s only the anions are assumed polarizable, while in the PIM2s both species are polarizable. Long molecular dynamics simulations show that the PIM2s is an unphysical model since, for some improbable but possible critical configurations, the ions become infinitely polarized. The results of using the PIM1, the PIM1s, as well as those of the simple RIM, have been compared for the static structure and ionic transport properties. The PIM1 reproduces the broad main peak of the total structure factor present in the neutron diffraction data, although the smoothed three-peak feature of this broad peak is slightly overestimated. The structural results for the PIM1s are intermediate between those for the RIM and the PIM1, but fail to reproduce the experimental features within the broad principal peak. Concerning the ionic transport properties, the value of the conductivity obtained using PIM1 is in good agreement with experimental values, while the self-diffusion coefficients and the conductivity for the PIM1s are lower than the corresponding values using the PIM1 and the RIM.