Subtlety of TiO2 phase stability: Reliability of the density functional theory predictions and persistence of the self-interaction error
Abstract
TiO2 is an important material with broad applications that can exist in different phases with dramatically different properties. Theoretical prediction of their polymorph energetics is therefore critical for the material design and for identifying thermodynamically accessible structures. Determining TiO2 relative phase stabilities remains challenging for first-principles methods, and density functional theory is the only approach available for studying phase stabilities at finite temperatures with acceptable computational efficiency. Here, we show that density functional theory using the recently developed efficient SCAN [Phys. Rev. Lett. 115, 036402 (2015)] exchange-correlation functional for the first time predicts the phase stability in qualitative agreement with the experimental results at realistic conditions. Further analysis shows that the self-interaction error intrinsic in the density functional persists in the stability prediction. By correcting the self-interaction error through an empirical approach, SCAN predicts the relative stability as well as defect properties in excellent agreement with the experimental results.
- Authors:
-
- Tulane Univ., New Orleans, LA (United States); Dept. of Physics and Engineering Physics
- Xi’an Jiaotong Univ., Xi’an (China). State Key Laboratory of Electric Insulation and Power Equipment
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Tulane Univ., New Orleans, LA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1543892
- Alternate Identifier(s):
- OSTI ID: 1737771
- Grant/Contract Number:
- SC023502; SC0019350
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 150; Journal Issue: 1; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics
Citation Formats
Zhang, Yubo, Furness, James W., Xiao, Bing, and Sun, Jianwei. Subtlety of TiO2 phase stability: Reliability of the density functional theory predictions and persistence of the self-interaction error. United States: N. p., 2019.
Web. doi:10.1063/1.5055623.
Zhang, Yubo, Furness, James W., Xiao, Bing, & Sun, Jianwei. Subtlety of TiO2 phase stability: Reliability of the density functional theory predictions and persistence of the self-interaction error. United States. https://doi.org/10.1063/1.5055623
Zhang, Yubo, Furness, James W., Xiao, Bing, and Sun, Jianwei. Mon .
"Subtlety of TiO2 phase stability: Reliability of the density functional theory predictions and persistence of the self-interaction error". United States. https://doi.org/10.1063/1.5055623. https://www.osti.gov/servlets/purl/1543892.
@article{osti_1543892,
title = {Subtlety of TiO2 phase stability: Reliability of the density functional theory predictions and persistence of the self-interaction error},
author = {Zhang, Yubo and Furness, James W. and Xiao, Bing and Sun, Jianwei},
abstractNote = {TiO2 is an important material with broad applications that can exist in different phases with dramatically different properties. Theoretical prediction of their polymorph energetics is therefore critical for the material design and for identifying thermodynamically accessible structures. Determining TiO2 relative phase stabilities remains challenging for first-principles methods, and density functional theory is the only approach available for studying phase stabilities at finite temperatures with acceptable computational efficiency. Here, we show that density functional theory using the recently developed efficient SCAN [Phys. Rev. Lett. 115, 036402 (2015)] exchange-correlation functional for the first time predicts the phase stability in qualitative agreement with the experimental results at realistic conditions. Further analysis shows that the self-interaction error intrinsic in the density functional persists in the stability prediction. By correcting the self-interaction error through an empirical approach, SCAN predicts the relative stability as well as defect properties in excellent agreement with the experimental results.},
doi = {10.1063/1.5055623},
journal = {Journal of Chemical Physics},
number = 1,
volume = 150,
place = {United States},
year = {Mon Jan 07 00:00:00 EST 2019},
month = {Mon Jan 07 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Electrochemical and Photoelectrochemical Investigation of Single-Crystal Anatase
journal, January 1996
- Kavan, L.; Grätzel, M.; Gilbert, S. E.
- Journal of the American Chemical Society, Vol. 118, Issue 28
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
corrected Hamiltonians for non-self-consistent random-phase approximation total-energy calculations: A study of ZnS, , and NiO
journal, January 2016
- Patrick, Christopher E.; Thygesen, Kristian S.
- Physical Review B, Vol. 93, Issue 3
Electronic absorption by Ti 3+ ions and electron delocalization in synthetic blue rutile
journal, May 1998
- Khomenko, V. M.; Langer, K.; Rager, H.
- Physics and Chemistry of Minerals, Vol. 25, Issue 5
Intrinsic n-type Defect Formation in TiO 2 : A Comparison of Rutile and Anatase from GGA+ U Calculations
journal, January 2010
- Morgan, Benjamin J.; Watson, Graeme W.
- The Journal of Physical Chemistry C, Vol. 114, Issue 5
Communication: Effect of the orbital-overlap dependence in the meta generalized gradient approximation
journal, August 2012
- Sun, Jianwei; Xiao, Bing; Ruzsinszky, Adrienn
- The Journal of Chemical Physics, Vol. 137, Issue 5
Electrical Properties and Defect Chemistry of TiO 2 Single Crystal. I. Electrical Conductivity †
journal, August 2006
- Nowotny, M. K.; Bak, T.; Nowotny, J.
- The Journal of Physical Chemistry B, Vol. 110, Issue 33
TiO 2 Stability Landscape: Polymorphism, Surface Energy, and Bound Water Energetics
journal, December 2006
- Levchenko, Andrey A.; Li, Guangshe; Boerio-Goates, Juliana
- Chemistry of Materials, Vol. 18, Issue 26
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997
- Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
Heat capacities and thermodynamic functions of TiO2 anatase and rutile: Analysis of phase stability
journal, February 2009
- Smith, S. J.; Stevens, R.; Liu, S.
- American Mineralogist, Vol. 94, Issue 2-3
Excess electron states in reduced bulk anatase TiO2: Comparison of standard GGA, GGA+U, and hybrid DFT calculations
journal, October 2008
- Finazzi, Emanuele; Di Valentin, Cristiana; Pacchioni, Gianfranco
- The Journal of Chemical Physics, Vol. 129, Issue 15
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional
journal, June 2016
- Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo
- Nature Chemistry, Vol. 8, Issue 9
Insights into Current Limitations of Density Functional Theory
journal, August 2008
- Cohen, A. J.; Mori-Sanchez, P.; Yang, W.
- Science, Vol. 321, Issue 5890
Synchrotron radiation studies of H2O adsorption on TiO2(110)
journal, August 1989
- Kurtz, Richard L.; Stock-Bauer, Roger; Msdey, Theodore E.
- Surface Science, Vol. 218, Issue 1
Efficient first-principles prediction of solid stability: Towards chemical accuracy
journal, March 2018
- Zhang, Yubo; Kitchaev, Daniil A.; Yang, Julia
- npj Computational Materials, Vol. 4, Issue 1
LDA + U and hybrid functional calculations for defects in ZnO, SnO2, and TiO2
journal, December 2010
- Janotti, Anderson; Van de Walle, Chris G.
- physica status solidi (b), Vol. 248, Issue 4
Adsorption and Photoinduced Decomposition of Acetone and Acetic Acid on Anatase, Brookite, and Rutile TiO 2 Nanoparticles
journal, July 2010
- Mattsson, A.; Österlund, L.
- The Journal of Physical Chemistry C, Vol. 114, Issue 33
DFT+U study of defects in bulk rutile TiO2
journal, October 2010
- Stausholm-Møller, Jess; Kristoffersen, Henrik H.; Hinnemann, Berit
- The Journal of Chemical Physics, Vol. 133, Issue 14
Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals
journal, November 2006
- Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I.
- The Journal of Chemical Physics, Vol. 125, Issue 19
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Investigating the Energetic Ordering of Stable and Metastable TiO 2 Polymorphs Using DFT+ U and Hybrid Functionals
journal, August 2015
- Curnan, Matthew T.; Kitchin, John R.
- The Journal of Physical Chemistry C, Vol. 119, Issue 36
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Energetics of nanocrystalline TiO2
journal, March 2002
- Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue Supplement 2
Localization and Delocalization Errors in Density Functional Theory and Implications for Band-Gap Prediction
journal, April 2008
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- Physical Review Letters, Vol. 100, Issue 14
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Many-electron self-interaction error in approximate density functionals
journal, November 2006
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- The Journal of Chemical Physics, Vol. 125, Issue 20
Titanium dioxide for solar-hydrogen II. Defect chemistry☆
journal, September 2007
- Nowotny, J.; Bak, T.; Nowotny, M.
- International Journal of Hydrogen Energy, Vol. 32, Issue 14
Titanium dioxide for solar-hydrogen I. Functional properties☆
journal, September 2007
- Nowotny, J.; Bak, T.; Nowotny, M.
- International Journal of Hydrogen Energy, Vol. 32, Issue 14
Density functional theory analysis of the structural and electronic properties of TiO2 rutile and anatase polytypes: Performances of different exchange-correlation functionals
journal, April 2007
- Labat, Frédéric; Baranek, Philippe; Domain, Christophe
- The Journal of Chemical Physics, Vol. 126, Issue 15
High mobility n ‐type charge carriers in large single crystals of anatase (TiO 2 )
journal, January 1994
- Forro, L.; Chauvet, O.; Emin, D.
- Journal of Applied Physics, Vol. 75, Issue 1
Insights into Photoexcited Electron Scavenging Processes on TiO 2 Obtained from Studies of the Reaction of O 2 with OH Groups Adsorbed at Electronic Defects on TiO 2 (110)
journal, January 2003
- Henderson, Michael A.; Epling, William S.; Peden, Charles H. F.
- The Journal of Physical Chemistry B, Vol. 107, Issue 2
Localized orbital scaling correction for systematic elimination of delocalization error in density functional approximations
journal, September 2017
- Li, Chen; Zheng, Xiao; Su, Neil Qiang
- National Science Review, Vol. 5, Issue 2
Structure of Nanocrystalline TiO 2 Powders and Precursor to Their Highly Efficient Photosensitizer
journal, February 1997
- Shklover, V.; Nazeeruddin, M. -K.; Zakeeruddin, S. M.
- Chemistry of Materials, Vol. 9, Issue 2
Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo
journal, November 2016
- Luo, Ye; Benali, Anouar; Shulenburger, Luke
- New Journal of Physics, Vol. 18, Issue 11
Communication: Self-interaction correction with unitary invariance in density functional theory
journal, March 2014
- Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P.
- The Journal of Chemical Physics, Vol. 140, Issue 12
Synchrotron radiation studies of H2O adsorption on TiO2(110)
journal, August 1989
- Kurtz, Richard L.; Stockbauer, Roger; Madey, Theodore E.
- Surface Science Letters, Vol. 218, Issue 1
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
An ultrasensitive molybdenum-based double-heterojunction phototransistor
text, January 2021
- , Feng; , Liu; , Zhu
- Zenodo
Oxygen Vacancies as Active Sites for Water Dissociation on Rutile TiO2(110)
text, January 2001
- Lopez, N.; Lægsgaard, E.; Schaub, R.
- The American Physical Society
First-principles DFT+GW study of oxygen vacancies in rutile TiO2
text, January 2014
- Malashevich, Andrei; Jain, Manish; Louie, Steven G.
- arXiv
Strongly Constrained and Appropriately Normed Semilocal Density Functional
preprint, January 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- arXiv
First principles phonon calculations in materials science
preprint, January 2015
- Togo, Atsushi; Tanaka, Isao
- arXiv
Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids
text, January 2003
- Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N.
- arXiv