Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile
Abstract
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.
- Authors:
-
- 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
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- California Inst. of Technology (CalTech), Pasadena, CA (United States)
- OSTI Identifier:
- 1265627
- Alternate Identifier(s):
- OSTI ID: 1209761
- Grant/Contract Number:
- FG02-03ER46055
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review. B, Condensed Matter and Materials Physics
- Additional Journal Information:
- Journal Volume: 92; Journal Issue: 5; Journal ID: ISSN 1098-0121
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Lan, Tian, Li, Chen W., Hellman, O., Kim, D. S., Muñoz, Jorge A., Smith, Hillary, Abernathy, Douglas L., and Fultz, B. Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2. United States: N. p., 2015.
Web. doi:10.1103/PhysRevB.92.054304.
Lan, Tian, Li, Chen W., Hellman, O., Kim, D. S., Muñoz, Jorge A., Smith, Hillary, Abernathy, Douglas L., & Fultz, B. Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2. United States. https://doi.org/10.1103/PhysRevB.92.054304
Lan, Tian, Li, Chen W., Hellman, O., Kim, D. S., Muñoz, Jorge A., Smith, Hillary, Abernathy, Douglas L., and Fultz, B. Tue .
"Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2". United States. https://doi.org/10.1103/PhysRevB.92.054304. https://www.osti.gov/servlets/purl/1265627.
@article{osti_1265627,
title = {Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO2},
author = {Lan, Tian and Li, Chen W. and Hellman, O. and Kim, D. S. and Muñoz, Jorge A. and Smith, Hillary and Abernathy, Douglas L. and Fultz, B.},
abstractNote = {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.},
doi = {10.1103/PhysRevB.92.054304},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 5,
volume = 92,
place = {United States},
year = {Tue Aug 11 00:00:00 EDT 2015},
month = {Tue Aug 11 00:00:00 EDT 2015}
}
Web of Science
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Works referencing / citing this record:
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