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Quantum Monte Carlo study of the energetics of the rutile, anatase, brookite, and columbite TiO2 polymorphs

John Trail, Bartomeu Monserrat, Pablo López Ríos, Ryo Maezono, and Richard J. Needs
Phys. Rev. B 95, 121108(R) – Published 27 March 2017
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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.

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  • Received 20 October 2016
  • Revised 26 January 2017

DOI:https://doi.org/10.1103/PhysRevB.95.121108

©2017 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

John Trail1,*, Bartomeu Monserrat1,2, Pablo López Ríos1, Ryo Maezono3, and Richard J. Needs1

  • 1Theory of Condensed Matter Group, Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom
  • 2Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854-8019, USA
  • 3School of Information Science, JAIST, Asahidai 1-1, Nomi, Ishikawa 923-1292, Japan

  • *jrt32@cantab.net

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Issue

Vol. 95, Iss. 12 — 15 March 2017

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