Free energies of ferroelectric crystals from a microscopic approach

DOI10.1016/J.CPC.2009.12.004zbMATH Open1205.82028arXiv0904.0264OpenAlexW1991036119MaRDI QIDQ615125FDOQ615125

Authors: Grégory Geneste 

Publication date: 5 January 2011

Published in: Computer Physics Communications (Search for Journal in Brave)

Abstract: The free energy of barium titanate is computed around the Curie temperature as a function of polarization from the first-principles derived effective hamiltonian of Zhong, Vanderbilt and Rabe [Phys. Rev. Lett. 73, 1861 (1994)], through Molecular Dynamics simulations coupled to the method of the Thermodynamic Integration. The main feature of this approach is to calculate the gradient of the free energy in the 3-D space (Px,Py,Pz) from the thermal averages of the forces acting on the local modes, that are obtained by Molecular Dynamics under the constraint of fixed P. A careful analysis of the states of constrained polarization is performed at T=280 K (~ 15-17 K below Tc) especially at low order parameter. These states are found reasonably homogeneous for small supercell size (L=12 and L=16), until inhomogeneous states are observed at low order parameter for large supercells (L=20). However, for reasonable supercell sizes (L=12), the free energy curves obtained are in very good agreement with phenomenological Landau potentials of the litterature. Moreover, the free energy obtained is quite insensitive to the supercell size from L=12 to L=16 at T=280 K, suggesting that interfacial contributions, if any, are negligible at these sizes around Tc. The method allows a numerical estimation of the free energy barrier separating the paraelectric from the ferroelectric phase at Tc. However, our tests evidence phase separation at low temperature and low order parameter, in agreement with the results of Tr"oster et al [Phys. Rev. B 72 (2005), 094103].

Full work available at URL: https://arxiv.org/abs/0904.0264

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zbMATH Keywords

thermodynamic integrationmolecular dynamicseffective Hamiltonianferroelectrics

Mathematics Subject Classification ID

Statistical thermodynamics (82B30) Statistical mechanics of ferroelectrics (82D45)

Cites Work

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Cited In (6)

• Title not available (Why is that?)
• Molecular statics simulations of ferroelectric barium titanate in the rhombohedral phase
• Deconfinement of electric charges in hydrogen-bonded ferroelectrics
• Fluctuations, higher anharmonisms, and the Ginzburg-Landau-Devonshire expansion for barium titanate
• Dynamical Matrices and Free Energies
• The Calculation of Free-Energiesin Semiconductors: Defects, Transitionsand Phase Diagrams

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