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Title: Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo

Abstract

Titanium dioxide, TiO2, has multiple applications in catalysis, energy conversion and memristive devices because of its electronic structure. Most of these applications utilize the naturally existing phases: rutile, anatase and brookite. Despite the simple form of TiO2 and its wide uses, there is long-standing disagreement between theory and experiment on the energetic ordering of these phases that has never been resolved. We present the first analysis of phase stability at zero temperature using the highly accurate many-body fixed node diffusion Quantum Monte Carlo (QMC) method. We also include the effects of temperature by calculating the Helmholtz free energy including both internal energy and vibrational contributions from density functional perturbation theory based quasi harmonic phonon calculations. Our QMC calculations find that anatase is the most stable phase at zero temperature, consistent with many previous mean-field calculations. However, at elevated temperatures, rutile becomes the most stable phase. For all finite temperatures, brookite is always the least stable phase.

Authors:
; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1333426
Alternate Identifier(s):
OSTI ID: 1333427; OSTI ID: 1334466; OSTI ID: 1364442
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
New Journal of Physics
Additional Journal Information:
Journal Name: New Journal of Physics Journal Volume: 18 Journal Issue: 11; Journal ID: ISSN 1367-2630
Publisher:
IOP Publishing
Country of Publication:
United Kingdom
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; 36 MATERIALS SCIENCE; titanium dioxide; phase stability; finite temperature; lattice dynamics; density functional theory; electronic structure; quantum Monte Carlo

Citation Formats

Luo, Ye, Benali, Anouar, Shulenburger, Luke, Krogel, Jaron T., Heinonen, Olle, and Kent, Paul R. C. Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo. United Kingdom: N. p., 2016. Web. doi:10.1088/1367-2630/18/11/113049.
Luo, Ye, Benali, Anouar, Shulenburger, Luke, Krogel, Jaron T., Heinonen, Olle, & Kent, Paul R. C. Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo. United Kingdom. https://doi.org/10.1088/1367-2630/18/11/113049
Luo, Ye, Benali, Anouar, Shulenburger, Luke, Krogel, Jaron T., Heinonen, Olle, and Kent, Paul R. C. Tue . "Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo". United Kingdom. https://doi.org/10.1088/1367-2630/18/11/113049.
@article{osti_1333426,
title = {Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo},
author = {Luo, Ye and Benali, Anouar and Shulenburger, Luke and Krogel, Jaron T. and Heinonen, Olle and Kent, Paul R. C.},
abstractNote = {Titanium dioxide, TiO2, has multiple applications in catalysis, energy conversion and memristive devices because of its electronic structure. Most of these applications utilize the naturally existing phases: rutile, anatase and brookite. Despite the simple form of TiO2 and its wide uses, there is long-standing disagreement between theory and experiment on the energetic ordering of these phases that has never been resolved. We present the first analysis of phase stability at zero temperature using the highly accurate many-body fixed node diffusion Quantum Monte Carlo (QMC) method. We also include the effects of temperature by calculating the Helmholtz free energy including both internal energy and vibrational contributions from density functional perturbation theory based quasi harmonic phonon calculations. Our QMC calculations find that anatase is the most stable phase at zero temperature, consistent with many previous mean-field calculations. However, at elevated temperatures, rutile becomes the most stable phase. For all finite temperatures, brookite is always the least stable phase.},
doi = {10.1088/1367-2630/18/11/113049},
journal = {New Journal of Physics},
number = 11,
volume = 18,
place = {United Kingdom},
year = {Tue Nov 01 00:00:00 EDT 2016},
month = {Tue Nov 01 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1088/1367-2630/18/11/113049

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Cited by: 45 works
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