In this paper, molecular models are used to investigate and analyze the polarization switching in the polyvinylidene fluoride (PVDF) and poly(vinylidene
fluoride-trifluoroethylene) (P(VDF-TrFE)) Langmuir-Blodgett (LB) nanofilms, in comparison with the experimental data at the nanoscale. Quantum-mechanical
calculations and modeling, as well as molecular dynamics (MD) simulations based on semi-empirical quantum-chemical methods (such as PM3), show that the energy
of the studied PVDF and P (VDF-TrFE) molecular structures, and their polarization switching proceed by the intrinsic homogeneous switching mechanism in
the framework of the phenomenological theory of Landau-Ginzburg-Devonshire (LGD) in the linear approximation at low values of the electric field.
The magnitude of the resulting critical coercive field is within the EC ~ 0.5 ... 2.5 GV/m, which is consistent with experimental data. It is also found
that the uniform polarization switching mechanism of the polymer chains PVDF and P (VDF-TrFE) is due to the quantum properties of the molecular orbitals
of the electron subsystem. This is clearly seen in both the polarization hysteresis loops, and the total energy changes. In this case, the turnover chain time,
obtained by molecular dynamics within semi-empirical quantum-chemical PM3 approach in a limited Hartree-Fock approximation, when approaching this critical
point, increases sharply, tending to infinity, which corresponds to the theory of LGD. Otherwise, at the high values of the applied electric field
the polarization switching correspond to the extrinsic domain mechanism in the frame of the microscopic Kolmogorov–Avrami–Ishibashi (KAI) theory, describing
bulk ferroelectric crystals and thick films. The performed analysis of computational and experimental data allows us to estimate the critical sizes of
the possible transition region approximately on the order of 10 nm between intrinsic homogeneous and extrinsic domain switching mechanisms.
Molecular dynamics study on the coalescence and break-up behaviors of ionic droplets under DC electric field
