A high-pressure Raman study of FeTiO3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer
Abstract
In this work, we investigated the 300 K high-pressure behavior of ilmenite using Raman spectroscopy to 54 GPa. Upon compression, we observe a Fermi resonance between the lowest frequency Ag symmetry peaks (ν4 and ν5) between ~ 10 and ~ 30 GPa: bands that involve major components of Ti–O and Fe–O-related displacements, respectively. The peaks’ relative intensities switch at ~ 18 GPa and they also reach their minimum separation at ~ 20 GPa, indicating that their maximum resonance occurs between 18 and 20 GPa. The negative shift of the Ti–O-associated ν4 vibration under compression is fully consistent with a shift in valence of Ti from 4 + to 3 + under compression. Anomalously small mode shifts of other, more localized vibrations are also consistent with a charge transfer from Fe to Ti under compression. At higher pressures, we have not found definitive evidence for a transition to the perovskite-structure at 300 K, which has been well characterized at high pressures and temperatures. At 40 GPa, we observe an apparent reversible disordering that persists up to our highest pressure. The 300 K mode shifts of the Raman active modes in FeTiO3 under pressure are notably different from those of other ABO3more »
- Authors:
-
- Univ. of Chicago, IL (United States); Univ. of Utah, Salt Lake City, UT (United States)
- Univ. of California, Santa Cruz, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
- OSTI Identifier:
- 1885118
- Report Number(s):
- LLNL-JRNL-824462
Journal ID: ISSN 0342-1791; 1037429
- Grant/Contract Number:
- AC52-07NA27344; EAR-1855336; EAR-1620423; EAR-2017294
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physics and Chemistry of Minerals
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 9; Journal ID: ISSN 0342-1791
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ilmenite; high pressure; Raman spectroscopy; Fermi resonance
Citation Formats
Vennari, Cara E., and Williams, Quentin. A high-pressure Raman study of FeTiO3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer. United States: N. p., 2021.
Web. doi:10.1007/s00269-021-01151-9.
Vennari, Cara E., & Williams, Quentin. A high-pressure Raman study of FeTiO3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer. United States. https://doi.org/10.1007/s00269-021-01151-9
Vennari, Cara E., and Williams, Quentin. Wed .
"A high-pressure Raman study of FeTiO3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer". United States. https://doi.org/10.1007/s00269-021-01151-9. https://www.osti.gov/servlets/purl/1885118.
@article{osti_1885118,
title = {A high-pressure Raman study of FeTiO3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer},
author = {Vennari, Cara E. and Williams, Quentin},
abstractNote = {In this work, we investigated the 300 K high-pressure behavior of ilmenite using Raman spectroscopy to 54 GPa. Upon compression, we observe a Fermi resonance between the lowest frequency Ag symmetry peaks (ν4 and ν5) between ~ 10 and ~ 30 GPa: bands that involve major components of Ti–O and Fe–O-related displacements, respectively. The peaks’ relative intensities switch at ~ 18 GPa and they also reach their minimum separation at ~ 20 GPa, indicating that their maximum resonance occurs between 18 and 20 GPa. The negative shift of the Ti–O-associated ν4 vibration under compression is fully consistent with a shift in valence of Ti from 4 + to 3 + under compression. Anomalously small mode shifts of other, more localized vibrations are also consistent with a charge transfer from Fe to Ti under compression. At higher pressures, we have not found definitive evidence for a transition to the perovskite-structure at 300 K, which has been well characterized at high pressures and temperatures. At 40 GPa, we observe an apparent reversible disordering that persists up to our highest pressure. The 300 K mode shifts of the Raman active modes in FeTiO3 under pressure are notably different from those of other ABO3 compounds (where A = Mg, Mn and B = Ti, Si); in other ilmenite-structured compounds, the peaks shift at a faster rate and there has not been any observation of Fermi resonance. Thus, iron’s complex electronic structure, and its charge transfer with titanium, appears to play a primary role in the behavior of phonons in FeTiO3 ilmenite.},
doi = {10.1007/s00269-021-01151-9},
journal = {Physics and Chemistry of Minerals},
number = 9,
volume = 48,
place = {United States},
year = {Wed Sep 01 00:00:00 EDT 2021},
month = {Wed Sep 01 00:00:00 EDT 2021}
}
Works referenced in this record:
Phase transformations and the constitution of the mantle
journal, January 1970
- Ringwood, A. E.
- Physics of the Earth and Planetary Interiors, Vol. 3
Thermal and Magmatic Evolution of the Moon
journal, January 2006
- Shearer, C. K.
- Reviews in Mineralogy and Geochemistry, Vol. 60, Issue 1
Iron-Titanium Oxide Minerals and Synthetic Equivalents
journal, January 1964
- Buddington, A. F.; Lindsley, D. H.
- Journal of Petrology, Vol. 5, Issue 2
Assignment of Raman-active vibrational modes of MgTiO3
journal, August 2008
- Wang, Chun-Hai; Jing, Xi-Ping; Feng, Wei
- Journal of Applied Physics, Vol. 104, Issue 3
Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite
journal, November 1989
- Ko, Jaidong; Brown, Nancy E.; Navrotsky, Alexandra
- Physics and Chemistry of Minerals, Vol. 16, Issue 8
The Raman spectra of several orthorhombic calcium oxide perovskites
journal, October 1988
- McMillan, Paul; Ross, Nancy
- Physics and Chemistry of Minerals, Vol. 16, Issue 1
High-pressure phase transition in brucite, Mg(OH) 2
journal, April 1995
- Duffy, Thomas S.; Meade, Charles; Fei, Yingwei
- American Mineralogist, Vol. 80, Issue 3-4
Tuning of the Fermi resonance of CO 2 and CS 2 by temperature, pressure, and matrix material
journal, April 1987
- Bier, K. D.; Jodl, H. J.
- The Journal of Chemical Physics, Vol. 86, Issue 8
High-pressure phase transition in MnTiO3 from the ilmenite to the LiNbO3 structure
journal, March 1988
- Ko, Jaidong; Prewitt, Charles T.
- Physics and Chemistry of Minerals, Vol. 15, Issue 4
High-pressure Raman spectroscopy and lattice-dynamics calculations on scintillating MgWO : Comparison with isomorphic compounds
journal, June 2011
- Ruiz-Fuertes, J.; Errandonea, D.; López-Moreno, S.
- Physical Review B, Vol. 83, Issue 21
An infrared and Raman spectroscopic study of PbSO4-anglesite at high pressures
journal, February 2019
- Sawchuk, Krista; O’Bannon, Earl F.; Vennari, Cara
- Physics and Chemistry of Minerals, Vol. 46, Issue 6
The role of hematite–ilmenite solid solution in the production of magnetic anomalies in ground- and satellite-based data
journal, March 2002
- Kletetschka, Gunther; Wasilewski, Peter J.; Taylor, Patrick T.
- Tectonophysics, Vol. 347, Issue 1-3
High-pressure perovskites on the join CaTiO3-FeTiO3
journal, June 1995
- Leinenweber, K.; Linton, J.; Navrotsky, A.
- Physics and Chemistry of Minerals, Vol. 22, Issue 4
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Unquenchable high-pressure perovskite polymorphs of MnSnO3 and FeTiO3
journal, December 1991
- Leinenweber, Kurt; Utsumi, Wataru; Tsuchida, Yoshihiko
- Physics and Chemistry of Minerals, Vol. 18, Issue 4
Calorimetric study of high pressure polymorphism in FeTiO3: Stability of the perovskite phase
journal, August 1994
- Mehta, Apurva; Leinenweber, Kurt; Navrotsky, Alexandra
- Physics and Chemistry of Minerals, Vol. 21, Issue 4
High-pressure transformations of ilmenite to perovskite, and lithium niobate to perovskite in zinc germanate
journal, March 2006
- Yusa, Hitoshi; Akaogi, Masaki; Sata, Nagayoshi
- Physics and Chemistry of Minerals, Vol. 33, Issue 3
Pressure induced Fe 2+ +Ti 4+ Fe 3+ +Ti 3+ intervalence charge transfer and the Fe 3+ /Fe 2+ ratio in natural ilmenite (FeTiO 3 ) minerals
journal, April 2004
- Seda, Takele; Hearne, G. R.
- Journal of Physics: Condensed Matter, Vol. 16, Issue 15
An infrared and Raman spectroscopic study of gypsum at high pressures
journal, October 2001
- Knittle, E.; Phillips, W.; Williams, Q.
- Physics and Chemistry of Minerals, Vol. 28, Issue 9
An infrared spectroscopic study of NH4Br —ammonium bromide to 55 GPa
journal, October 2006
- Reed, J. W.; Williams, Q.
- Solid State Communications, Vol. 140, Issue 3-4
Variable-temperature and -pressure spectroscopic studies of norbornadiene
journal, July 1990
- Kawai, N. T.; Gilson, D. F. R.; Butler, I. S.
- The Journal of Physical Chemistry, Vol. 94, Issue 15
Single crystal X-ray and M�ssbauer study of shocked ilmenite to 80 GPa
journal, March 1981
- Syono, Yasuhiko; Takei, Humihiko; Goto, Tsuneaki
- Physics and Chemistry of Minerals, Vol. 7, Issue 2
Investigation into high-pressure behavior of MnTiO3: X-ray diffraction and Raman spectroscopy with diamond anvil cells
journal, January 2011
- Wu, Xiang; Qin, Shan; Dubrovinsky, Leonid
- Geoscience Frontiers, Vol. 2, Issue 1
Raman spectroscopic constraints on compression and metastability of the amphibole tremolite at high pressures and temperatures
journal, May 2020
- Ott, Jason N.; Williams, Quentin
- Physics and Chemistry of Minerals, Vol. 47, Issue 6
High-pressure and high-temperature phase transitions in FeTiO3 and a new dense FeTi3O7 structure
journal, March 2012
- Nishio-Hamane, D.; Zhang, M.; Yagi, T.
- American Mineralogist, Vol. 97, Issue 4
High-pressure Raman spectroscopic studies of FeS 2 pyrite
journal, June 2004
- Kleppe, A. K.; Jephcoat, A. P.
- Mineralogical Magazine, Vol. 68, Issue 3
X-ray diffraction study of the phase transitions and structural evolution of tin dioxide at high pressure:ffRelationships between structure types and implications for other rutile-type dioxides
journal, May 1997
- Haines, J.; Léger, J. M.
- Physical Review B, Vol. 55, Issue 17
The effect of ilmenite viscosity on the dynamics and evolution of an overturned lunar cumulate mantle: Ilmenite Effects on the Lunar Upwellings
journal, July 2017
- Zhang, Nan; Dygert, Nick; Liang, Yan
- Geophysical Research Letters, Vol. 44, Issue 13
Raman study of thaumasite Ca3Si(OH)6(SO4)(CO3)⋅12H2O at high pressure
journal, May 2016
- Goryainov, S. V.
- Journal of Raman Spectroscopy, Vol. 47, Issue 8
1. The power of databases: The RRUFF project
book, November 2015
- Lafuente, Barbara; Downs, R. T.; Yang, H.
- Highlights in Mineralogical Crystallography
Correction to “Vibrational spectrum of MgSiO3perovskite: Zero-pressure Raman and mid-infrared spectra to 27 GPa” by Quentin Williams, Raymond Jeanloz, and Paul McMillan
journal, October 1987
- Williams, Quentin; Jeanloz, Raymond; McMillan, Paul
- Journal of Geophysical Research: Solid Earth, Vol. 92, Issue B11
Structure change of MgSiO3, MgGeO3, and MgTiO3 ilmenites under compression
journal, August 2005
- Yamanaka, T.
- American Mineralogist, Vol. 90, Issue 8-9
Effect of pressure and temperature on the Raman spectra of solid CO 2
journal, April 1988
- Olijnyk, H.; Däufer, H.; Jodl, H. ‐J.
- The Journal of Chemical Physics, Vol. 88, Issue 7
On the Vibrational Spectra and Structure of FeCrO3 and of the Ilmenite-Type Compounds CoTiO3 and NiTiO3
journal, September 1994
- Baraton, M. I.; Busca, G.; Prieto, M. C.
- Journal of Solid State Chemistry, Vol. 112, Issue 1
In situ X-ray diffraction study of phase transitions of FeTiO 3 at high pressures and temperatures using a large-volume press and synchrotron radiation
journal, January 2006
- Ming, Li Chung; Kim, Young-Ho; Uchida, T.
- American Mineralogist, Vol. 91, Issue 1
A note on the structure of lithium niobate, LiNbO3
journal, November 1968
- Megaw, H. D.
- Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 24, Issue 6
Structural characterization of the FeTiO3–MnTiO3 solid solution
journal, October 2010
- Wu, Xiang; Qin, Shan; Dubrovinsky, Leonid
- Journal of Solid State Chemistry, Vol. 183, Issue 10
IR reflectance spectra of natural ilmenite: comparison with isostructural compounds and calculation of thermodynamic properties [IR reflectance spectra of natural ilmenite: comparison with isostructural compounds and calculation of thermodynamic properties]
journal, April 1993
- Hofmeister, Anne M.
- European Journal of Mineralogy, Vol. 5, Issue 2
Iron oxidation state ofFeTiO 3 under high pressure
journal, March 2009
- Wu, X.; Steinle-Neumann, G.; Narygina, O.
- Physical Review B, Vol. 79, Issue 9
Comparative Raman spectroscopic study on ilmenite-type MgSiO3 (akimotoite), MgGeO3, and MgTiO3 (geikielite) at high temperatures and high pressures
journal, January 2008
- Okada, T.; Narita, T.; Nagai, T.
- American Mineralogist, Vol. 93, Issue 1
Pressure-tuning resonance between the vibron and the libron inCH 2 Br 2 andCD 2 Br 2 molecular solids
journal, September 1985
- Shimizu, H.
- Physical Review B, Vol. 32, Issue 6