A particularly attractive method to predict the dielectric properties of materials is density functional theory (DFT). While this method is very popular, its large computational requirements allow practical treatments of unit cells with just a small number of atoms in an ordered array, i.e., in a crystalline morphology. By comparing DFT and Molecular Dynamics (MD) simulations on the same ordered arrays of functional polyolefins, we confirm that both methodologies yield identical estimates for the dipole moments and hence the ionic component of the dielectric storage modulus. Additionally, MD simulations of more realistic semi-crystalline morphologies yield estimates for this polar contribution that are in good agreement with the limited experiments in this field. However, these predictions are up to 10 times larger than those for pure crystalline simulations. Here, we show that the constraints provided by the surrounding chains significantly impede dipolar relaxations in the crystalline regions, whereas amorphous chains must sample all configurations to attain their fully isotropic spatial distributions. These results, which suggest that the amorphous phase is the dominant player in the context, argue strongly that the proper polymer morphology needs to be modeled to ensure accurate estimates of the ionic component of the dielectric constant.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry