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Predicting phase transitions in PbTi⁢O3 using zentropy through quasiharmonic phonon calculations

Journal Article · · Physical Review. B
 [1];  [1];  [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
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According to x-ray diffraction (XRD) measurements, PbTi⁢O3 undergoes a phase transition from a tetragonal ferroelectric (FE) phase to a cubic paraelectric phase at 763 K. However, x-ray absorption fine-structure (XAFS) measurements indicate that PbTi⁢O3 is locally tetragonal even after the phase transition. The difference in these results is because XAFS measurements can probe local features of a structure, while XRD averages over such local features. For both measurements to be consistent, PbTi⁢O3 is macroscopically cubic but locally tetragonal after the phase transition. Despite this, most models, such as the Landau-Ginsburg-Devonshire theory and effective Hamiltonians, are still unable to explain this phenomenon. Moreover, these methods involve model parameters fitted to experimental or theoretical data and do not consider other tetragonal configurations, such as domain walls, to predict the phase transition. In our previous study, we used our zentropy approach to predict the phase transition by considering the tetragonal FE ground-state configuration and the tetragonal 90° and 180° domain wall configurations with their total energies at 0 K. Here, in this paper, the Helmholtz energies of the three configurations are obtained from density functional theory calculations through energy-volume curves and phonon calculations. The predicted phase transition temperature using the meta-GGA 𝑟2⁢SCAN and revised multiplicities of configurations is 716 K, showing good agreement with the experimental value of 763 K.
Research Organization:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0023185
OSTI ID:
3022567
Alternate ID(s):
OSTI ID: 2477099
Journal Information:
Physical Review. B, Journal Name: Physical Review. B Journal Issue: 18 Vol. 110; ISSN 2469-9969; ISSN 2469-9950
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (63)

Magnetic excitation and thermodynamics of BaFe2As2 journal January 2010
Zentropy Theory for Positive and Negative Thermal Expansion journal February 2022
Dielectric and elastic properties of ferroelectric materials at elevated temperature journal October 1996
The ferroelectric phase transition in PbTiO3 from a local perspective journal March 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
DFTTK: Density Functional Theory ToolKit for high-throughput lattice dynamics calculations journal December 2021
First-principles thermodynamics from phonon and Debye model: Application to Ni and Ni3Al journal February 2010
Extensible Structure-Informed Prediction of Formation Energy with improved accuracy and usability employing neural networks journal June 2022
YPHON: A package for calculating phonons of polar materials journal November 2014
Density functional thermodynamic description of spin, phonon and displacement degrees of freedom in antiferromagnetic-to-paramagnetic phase transition in YNiO3 journal October 2022
Recent advances in percolation theory and its applications journal May 2015
Quantifying the degree of disorder and associated phenomena in materials through zentropy: Illustrated with Invar Fe3Pt journal March 2023
Parameter-free prediction of phase transition in PbTiO3 through combination of quantum mechanics and statistical mechanics journal July 2023
Note on Exchange Phenomena in the Thomas Atom journal July 1930
Accurate and Numerically Efficient r 2 SCAN Meta-Generalized Gradient Approximation journal September 2020
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional journal June 2016
Highly charged 180 degree head-to-head domain walls in lead titanate journal December 2020
Thermal Expansion Anomaly Regulated by Entropy journal November 2014
Thermodynamic theory of PbTiO 3 journal October 1987
Magnetic thermodynamics of fcc Ni from first-principles partition function approach journal December 2010
Thermal equations of state and phase relation of PbTiO 3 : A high P-T synchrotron x-ray diffraction study journal October 2011
Assessing r2SCAN meta-GGA functional for structural parameters, cohesive energy, mechanical modulus, and thermophysical properties of 3d, 4d, and 5d transition metals journal January 2024
The ferroelectric and cubic phases in BaTiO3 ferroelectrics are also antiferroelectric journal September 2006
Theory of the electric polarization in crystals journal November 1992
Order-disorder behavior in the phase transition of PbTiO3 journal February 1995
Atomistic structure of 90° domain walls in ferroelectric PbTiO 3 thin films journal March 1995
Thermodynamic fluctuations in magnetic states: Fe 3 Pt as a prototype journal December 2010
XCVI. Theory of barium titanate: Part I journal October 1949
Theory of cross phenomena and their coefficients beyond Onsager theorem journal April 2022
A thermodynamic framework for a system with itinerant-electron magnetism journal July 2009
Structure and energetics of 180° domain walls in PbTiO 3 by density functional theory journal April 2011
Interplay of domain structure and phase transitions: theory, experiment and functionality journal November 2021
Diffraction contrast analysis of 90° and 180° ferroelectric domain structures of PbTiO 3 thin films journal June 2011
Principles and Applications of Ferroelectrics and Related Materials book February 2001
A comparison of HREM and weak beam transmission electron microscopy for the quantitative measurement of the thickness of ferroelectric domain walls journal January 1999
First-principles study of two-dimensional electron and hole gases at the head-to-head and tail-to-tail 180 ∘ domain walls in PbTiO 3 ferroelectric thin films journal May 2020
Intrinsic local symmetry breaking in nominally cubic paraelectric BaTiO3 journal June 2022
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Nature of the ferroelectric phase transition in PbTiO 3 journal November 1994
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Ab initio statistical mechanics of the ferroelectric phase transition in PbTiO 3 journal March 1997
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Ab initio study of ferroelectric domain walls in PbTiO 3 journal March 2002
Ab initio study of stress-induced domain switching in Pb Ti O 3 journal March 2008
Hybrid exchange-correlation functional for accurate prediction of the electronic and structural properties of ferroelectric oxides journal April 2008
Thermodynamics of the Ce γ – α transition: Density-functional study journal September 2008
Domain walls of ferroelectric BaTiO 3 within the Ginzburg-Landau-Devonshire phenomenological model journal April 2010
Thermodynamic fluctuations between magnetic states from first-principles phonon calculations: The case of bcc Fe journal July 2010
Domain formation and dielectric response in PbTiO 3 : A first-principles free-energy landscape analysis journal January 2013
Nature of ferroelectric-paraelectric phase transition and origin of negative thermal expansion in PbTi O 3 journal January 2015
Second-principles method for materials simulations including electron and lattice degrees of freedom journal May 2016
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
Ground State of the Electron Gas by a Stochastic Method journal August 1980
Phase Transitions in BaTi O 3 from First Principles journal September 1994
Comparative study of Minnesota functionals performance on ferroelectric BaTiO 3 and PbTiO 3 journal July 2020
Performance comparison of r 2 SCAN and SCAN metaGGA density functionals for solid materials via an automated, high-throughput computational workflow journal January 2022
Topics in electronic ceramics journal January 1990
On the Phase Transition in Lead Titanate journal July 1951
A Theory of Ferroelectric 90 Degree Domain Wall journal November 2002
First-Principles Statistical Mechanics of Multicomponent Crystals journal July 2018
Zentropy theory for accurate prediction of free energy, volume, and thermal expansion without fitting parameters journal January 2024
First-principles Phonon Calculations with Phonopy and Phono3py journal January 2023

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Related Subjects

36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
PbTiO3
density functional theory
ferroelectrics
phase transitions
quantum statistical mechanics
zentropy