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Quantum Monte Carlo study of the energetics of the rutile, anatase, brookite, and columbite TiO$_{2}$ polymorphs

Accepted version
Peer-reviewed

Type

Article

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Authors

Monserrat, B 
López Ríos, P 
Maezono, R 
Needs, RJ 

Abstract

The relative energies of the low-pressure rutile, anatase, and brookite polymorphs and the high-pressure columbite polymorph of TiO2 have been calculated as a function of temperature using the diffusion quantum Monte Carlo (DMC) method and density functional theory (DFT). The vibrational energies are found to be important on the scale of interest and significant quartic anharmonicity is found in the rutile phase. Static-lattice DFT calculations predict that anatase is lower in energy than rutile, in disagreement with experiment. The accurate description of electronic correlations afforded by DMC calculations and the inclusion of anharmonic vibrational effects contribute to stabilizing rutile with respect to anatase. Our calculations predict a phase transition from anatase to rutile TiO2 at 630±210 K.

Description

Keywords

cond-mat.mtrl-sci, cond-mat.mtrl-sci

Journal Title

Physical Review B

Conference Name

Journal ISSN

2469-9950
2469-9969

Volume Title

95

Publisher

American Physical Society
Sponsorship
Engineering and Physical Sciences Research Council (EP/J017639/1)
Engineering and Physical Sciences Research Council (EP/K014560/1)
Engineering and Physical Sciences Research Council (EP/P022596/1)
Engineering and Physical Sciences Research Council (EP/F032773/1)
J.R.T., P.L.R., and R.J.N. acknowledge financial support from the Engineering and Physical Sciences Research Council (EPSRC) of the U.K. under Grant No. EP/J017639/1. B.M. acknowledges support from Robinson College, Cambridge, and the Cambridge Philosophical Society for a Henslow Research Fellowship. R.M. is grateful for financial support from MEXT-KAKENHI Grants No. 26287063, No. 25600156, and No. 22104011, and a grant from the Asahi Glass Foundation. Computational resources were provided by the Archer facility of the U.K.'s national high-performance computing service (for which access was obtained via the UKCP consortium, EPSRC Grant No. EP/K014560/1), by the Center for Information Science of the JAIST, and by the K-computer (supported by the Computational Materials Science Initiative, CMSI/Japan, under Projects No. hp120086, No. hp140150, and No. hp150014).
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