Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2

Lan, Tian; Li, Chen W.; Hellman, O.; Kim, D. S.; Muñoz, Jorge A.; Smith, Hillary; Abernathy, Douglas L.; Fultz, B.

doi:10.1103/PhysRevB.92.054304

Title: Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile ${TiO}_{2}$

Journal Article · Tue Aug 11 00:00:00 EDT 2015 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.92.054304· OSTI ID:1265627

Lan, Tian ^[1]; Li, Chen W. ^[2]; Hellman, O. ^[1]; Kim, D. S. ^[1]; Muñoz, Jorge A. ^[1]; Smith, Hillary ^[1]; Abernathy, Douglas L. ^[3]; Fultz, B. ^[1]

California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Applied Physics and Materials Science
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division

Although the rutile structure of TiO₂ is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000 K. In this paper, inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO₂ from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: California Inst. of Technology (CalTech), Pasadena, CA (United States)

Grant/Contract Number:: FG02-03ER46055

OSTI ID:: 1265627

Alternate ID(s):: OSTI ID: 1209761

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Vol. 92, Issue 5; ISSN 1098-0121

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Quantum Monte Carlo study of the energetics of the rutile, anatase, brookite, and columbite TiO$_{2}$ polymorphs Trail, John; Monserrat Sanchez, Bartomeu; López Ríos, P. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.9937	text	January 2017

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