First-principles accurate total-energy surfaces for polar structural distortions of BaTiO3, PbTiO3, and SrTiO3: consequences to structural transition temperatures

Abstract

Specific forms of the exchange correlation energy functionals in first-principles density functional theory-based calculations, such as the local density approximation (LDA) and generalized-gradient approximations (GGA), give rise to structural lattice parameters with typical errors of -2% and 2%. Due to a strong coupling between structure and polarization, the order parameter of ferroelectric transitions, they result in large errors in estimation of temperature dependent ferroelectric structural transition properties. Here, we employ a recently developed GGA functional of Wu and Cohen [Phys. Rev. B 73, 235116 (2006)] and determine total-energy surfaces for zone-center distortions of BaTiO3, PbTiO3, and SrTiO3, and compare them with the ones obtained with calculations based on standard LDA and GGA. Confirming that the Wu and Cohen functional allows better estimation of structural properties at 0 K, we determine a new set of parameters defining the effective Hamiltonian for ferroelectric transition in BaTiO3. Using the new set of parameters, we perform molecular-dynamics (MD) simulations under effective pressures p=0.0 GPa, p=-2.0 GPa, and p=-0.005T GPa. The simulations under p=-0.005T GPa, which is for simulating thermal expansion, show a clear improvement in the cubic to tetragonal transition temperature and c/a parameter of its ferroelectric tetragonal phase, while the description of transitions at lower temperatures to orthorhombic and rhombohedral phases is marginally improved. Our findings augur well for use of Wu-Cohen functional in studies of ferroelectrics at nano-scale, particularly in the form of epitaxial films where the properties depend crucially on the lattice mismatch.

10 pages, 7 figures, 3 tables, resubmitted to PRB

References in corpus (8)

• Separable Dual Space Gaussian Pseudo-potentials
• A More Accurate Generalized Gradient Approximation for Solids
• First-principles theory of ferroelectric phase transitions for perovskites: The case of BaTiO3
• Hybrid exchange-correlation functional for accurate prediction of the electronic and structural properties of ferroelectric oxides
• Ab initio statistical mechanics of the ferroelectric phase transition in PbTiO3
• Fast Molecular-Dynamics Simulation for Ferroelectric Thin-Film Capacitors Using a First-Principles Effective Hamiltonian
• Quantitative analysis of the first-principles effective-Hamiltonian approach to ferroelectric perovskites
• Ab initio Study of Valley Line on a Total-Energy Surface for Zone-Center Distortions of Ferroelectric Perovskite Oxides BaTiO3 and PbTiO3

Cited by in corpus (32)

• Structure and properties of functional oxide thin films: Insights from electronic-structure calculations
• First principles-based calculation of the electrocaloric effect in BaTiO${}_3$: comparison between direct and indirect methods
• The electrocaloric effect in BaTiO${}_3$ at all three ferroelectric transitions: anisotropy and inverse caloric effects
• Influence of defects on ferroelectric and electrocaloric properties of BaTiO${}_3$
• Correlated local dipoles in PbTe
• Positive and negative electrocaloric effect in BaTiO${}_3$ in the presence of defect dipoles
• Efficient thermoelectric materials using nonmagnetic double perovskites with $d^0$/$d^6$ band filling
• Electrocaloric effect in BaTiO${}_3$: a first-principles-based study on the effect of misfit strain
• Direct molecular dynamics simulation of electrocaloric effect in BaTiO3
• Charge effects in donor doped perovskite ferroelectrics
• First-Principles-Based Strain and Temperature Dependent Ferroic Phase Diagram of SrMnO${}_3$
• Electrostriction coefficient of ferroelectric materials from ab initio computation
• Ab initio phase diagram of BaTiO${}_3$ under epitaxial strain revisited
• Ewald summation for ferroelectric perovskites with charges and dipoles
• Understanding doped perovskite ferroelectrics with defective dipole model
• Active learning of effective Hamiltonian for super-large-scale atomic structures
• Tailoring the electrocaloric effect by internal bias fields and field protocols
• Molecular Dynamics Simulations of Chemically Disordered Ferroelectric (Ba,Sr)TiO${}_3$ with a Semi-Empirical Effective Hamiltonian
• The impact of hysteresis on the electrocaloric effect at first-order phase transitions
• Giant Magnetoelastic Effects in BaTiO3-based Extrinsic Multiferroic Hybrids
• A first-principles study of structural and elastic properties of bulk SrRuO${}_3$
• Control of ferroelectric domain wall dynamics by point defects: Insights from ab initio based simulations
• Domain Wall Acceleration by Ultrafast Field Application: An Ab Initio-Based Molecular Dynamics Study
• Thermal stability of nano-scale ferroelectric domains by molecular dynamics modeling
• Tuning the caloric response of BaTiO${}_3$ by tensile epitaxial strain
• Impact of domains on the orthorhombic-tetragonal transition of BaTiO${}_3$: an ab initio study
• Epitaxially strained SnTiO${}_3$ at finite temperatures
• Electric field direction dependence of the electrocaloric effect in BaTiO3
• Thermal Stability and Topological Charge Fragmentation in Antiskyrmions of Rhombohedral Barium Titanate
• BaTiO${}_3$ -- SrTiO${}_3$ composites: a microscopic study on paraelectric cubic inclusions
• Topological Textures in Zr-Substituted Barium Titanate
• Effective Hamiltonian Methods for Predicting the Electrocaloric Behavior of BaTiO3