Electric field control of proton-transfer molecular switching: molecular dynamics study on salicylidene aniline

2015 ◽  
Vol 17 (22) ◽  
pp. 14484-14488 ◽  
Author(s):  
Joanna Jankowska ◽  
Joanna Sadlej ◽  
Andrzej L. Sobolewski
Keyword(s):  
Molecular Dynamics ◽  
Electric Field ◽  
Proton Transfer ◽  
Intramolecular Proton Transfer ◽  
Molecular Switch ◽  
Molecular Switching ◽  
Switching Mechanism ◽  
Field Control

In this letter, we propose a novel, ultrafast, efficient molecular switch whose switching mechanism involves the electric field-driven intramolecular proton transfer.

Анализ вычислительных и экспериментальных исследований переключения поляризации в ПВДФ и П (ВДФ-ТрФЭ) сегнетоэлектрических пленках на наноуровне

2015 ◽  
Vol 10 (2) ◽  
pp. 372-386 ◽  
Author(s):  
В.С. Быстров ◽  
V.S. Bystrov
Keyword(s):  
Experimental Data ◽  
Molecular Dynamics ◽  
Electric Field ◽  
Quantum Chemical ◽  
Polyvinylidene Fluoride ◽  
Domain Switching ◽  
Polarization Switching ◽  
Molecular Structures ◽  
Switching Mechanism ◽  
Semi Empirical

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.

Computer modeling and molecular dynamics of polarization switching in the ferroelectric films PVDF and P(VDF-TrFE) on nanoscale

2015 ◽  
Vol 10 (1) ◽  
pp. 131-153 ◽  
Author(s):  
В.Е. Геворкян ◽  
V.E. Gevorkyan
Keyword(s):  
Molecular Dynamics ◽  
Electric Field ◽  
Total Energy ◽  
Critical Point ◽  
Quantum Chemical ◽  
Polarization Switching ◽  
Total System ◽  
Switching Mechanism ◽  
Gradual Shift ◽  
Semi Empirical

In this paper, molecular models are used to investigate and analyze the structure and polarization of polyvinylidene fluoride (PVDF) and poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) Langmuir-Blodgett (LB) nanofilms, depending on the structure and composition of the monomers of their polymer and copolymer chains. 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 homogeneous switching mechanism in the framework of the phenomenological theory of Landau-Ginzburg-Devonshire (LGD) in the linear approximation of low values of the electric field. The magnitude of the resulting critical coercive field is within the EC ~ 0.5 ... 2.0 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: the applied electric field induces a gradual shift of the electron "clouds" density (electron polarizability), which in turn causes a gradual shift of the nuclear cores, in accordance with the principle of minimum total energy of the system, and this leads eventually, when it reaches a critical point (bifurcation) - to overturn of the entire chain and a sharp decrease in the total energy of the total system to its energetically more favorable state. 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.

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