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Title: X-ray photoelectron spectra for single-crystal Ti2O3: experiment and theory

Abstract

We have measured high-resolution core-level and valence band x-ray photoemission spectra for single-crystal Ti2O3 cleaved anoxically. The Ti3+ spectra for this lattice are considerably more complex than those measured for Ti4+- based oxides due to the presence of a single unpaired electron in the conduction band. The Ti 2p and 3p spectra have been determined from relativistic Dirac-Hartree-Fock (DHF) theory using the sudden approximation for the XPS intensities. Agreement between theory and experiment is excellent for the 3p spectrum, and very good for the 2p spectrum, the primary deficiency being a pair of features not captured by theory for the latter. The spectral line shapes are driven by final-state effects associated with angular momentum coupling of the unpaired valence electron with the core hole, one- and two-electron ligand-to-metal charge transfer (shake) processes accompanying core photoionization, and core-hole screening by conduction band electrons. The first two of these are accurately predicted by DHF theory with a small embedded cluster containing a single Ti cation and six oxygen ligands. The third effect is not predicted using this cluster in which screening of the core-hole from electrons associated with more distant atoms is not possible.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [2];  [3];  [2];  [4];  [5];  [6]
  1. BATTELLE (PACIFIC NW LAB)
  2. State University of New York at Binghamton
  3. National Institute of Standards and Technology
  4. Diamond Light Source, Ltd.
  5. Consultant
  6. UNIVERSITY OF NORTH TEXAS
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1523813
Report Number(s):
PNNL-SA-127619
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 96; Journal Issue: 20
Country of Publication:
United States
Language:
English

Citation Formats

Chambers, Scott A., Engelhard, Mark H., Wang, Le, Droubay, Timothy C., Bowden, Mark E., Wahila, M J., Quackenbush, Nicholas, Piper, Louis F. J., Lee, Tien-Lin, Nelin, Connie J., and Bagus, Paul S. X-ray photoelectron spectra for single-crystal Ti2O3: experiment and theory. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.96.205143.
Chambers, Scott A., Engelhard, Mark H., Wang, Le, Droubay, Timothy C., Bowden, Mark E., Wahila, M J., Quackenbush, Nicholas, Piper, Louis F. J., Lee, Tien-Lin, Nelin, Connie J., & Bagus, Paul S. X-ray photoelectron spectra for single-crystal Ti2O3: experiment and theory. United States. doi:10.1103/PhysRevB.96.205143.
Chambers, Scott A., Engelhard, Mark H., Wang, Le, Droubay, Timothy C., Bowden, Mark E., Wahila, M J., Quackenbush, Nicholas, Piper, Louis F. J., Lee, Tien-Lin, Nelin, Connie J., and Bagus, Paul S. Wed . "X-ray photoelectron spectra for single-crystal Ti2O3: experiment and theory". United States. doi:10.1103/PhysRevB.96.205143.
@article{osti_1523813,
title = {X-ray photoelectron spectra for single-crystal Ti2O3: experiment and theory},
author = {Chambers, Scott A. and Engelhard, Mark H. and Wang, Le and Droubay, Timothy C. and Bowden, Mark E. and Wahila, M J. and Quackenbush, Nicholas and Piper, Louis F. J. and Lee, Tien-Lin and Nelin, Connie J. and Bagus, Paul S.},
abstractNote = {We have measured high-resolution core-level and valence band x-ray photoemission spectra for single-crystal Ti2O3 cleaved anoxically. The Ti3+ spectra for this lattice are considerably more complex than those measured for Ti4+- based oxides due to the presence of a single unpaired electron in the conduction band. The Ti 2p and 3p spectra have been determined from relativistic Dirac-Hartree-Fock (DHF) theory using the sudden approximation for the XPS intensities. Agreement between theory and experiment is excellent for the 3p spectrum, and very good for the 2p spectrum, the primary deficiency being a pair of features not captured by theory for the latter. The spectral line shapes are driven by final-state effects associated with angular momentum coupling of the unpaired valence electron with the core hole, one- and two-electron ligand-to-metal charge transfer (shake) processes accompanying core photoionization, and core-hole screening by conduction band electrons. The first two of these are accurately predicted by DHF theory with a small embedded cluster containing a single Ti cation and six oxygen ligands. The third effect is not predicted using this cluster in which screening of the core-hole from electrons associated with more distant atoms is not possible.},
doi = {10.1103/PhysRevB.96.205143},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 20,
volume = 96,
place = {United States},
year = {2017},
month = {11}
}

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