Dielectric Constant Calculation of Poly(vinylidene fluoride) Based on Finite Field and Density Functional Theory

In this study, we proposed a novel method that integrates density functional theory (DFT) with the finite field method to accurately estimate the polarizability and dielectric constant of polymers. Our approach effectively accounts for the influence of electronic and geometric conformation changed on the dielectric constant. We validated our method using polyethylene (PE) and polytetrafluoroethylene (PTFE) as benchmark materials, and found that it reliably predicted their dielectric constants. Furthermore, we explored the impact of conformation variations in poly(vinylidene fluoride) (PVDF) on its dielectric constant and polarizability. The resulting dielectric constants of α- and γ-PVDF (3.0) showed excellent agreement with crystalline PVDF in experiments. Our findings illuminate the relationship between PVDF’s structural properties and its electrical behavior, offering valuable insights for material design and applications.