Contributions of Rotational and Collective Translational Dipole Moments to Dielectric Constants in Polymeric Ionic Liquids: A Coarse-Grained Stockmayer Molecular Dynamics Study

Molecular polarization in polymeric ionic liquids comprises both rotational and collective translational dipole moments of their monomeric units. While standard dielectric theories typically account for the rotational component, the influence of the translational component on dielectric properties remains unclear. In this study, we investigate how electrostatic correlations among ion-ion, ion-dipole, and dipole-dipole interactions affect these molecular polarizations and the resulting dielectric constants. Using coarse-grained Stockmayer fluid (SF) molecular dynamics models for poly(1-ethyl-3-vinylimidazolium bis(trifluoromethane sulfonyl imide)), our simulations reveal that, unlike uncharged solvents, both rotational and translational dipole contributions are equally significant in determining the total dielectric constant.