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Title: Extended X-Ray Absorption Fine Structure of ZrW2O8: Theory vs. Experiment

Abstract

Extended x-ray absorption fine structure (EXAFS) is well-suited for investigations of structure and disorder of complex materials. Recently, experimental measurements and analysis of EXAFS have been carried out to elucidate the mechanisms responsible for the negative thermal expansion (NTE) in zirconium tungstate (ZrW 2O 8). In contrast to previous work suggesting that transverse O-displacements are largely responsible, the EXAFS analysis suggested that correlated rotations and translations of octahedra and tetrahedra within the structure are a major source. In an effort to resolve this controversy, we have carried out ab initio calculations of the structure, lattice vibrations, and EXAFS of ZrW 2O 8 based on real-space multiple-scattering calculations using the FEFF9 code and auxiliary calculations of structure and Debye-Waller factors. We find that the theoretical simulations are consistent with observed EXAFS, and show that both of the above mechanisms contribute to the dynamical structure of ZrW 2O 8.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States); Univ. of California, Santa Cruz, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466058
Alternate Identifier(s):
OSTI ID: 1510434
Grant/Contract Number:  
FG02-03ER15476; AC02-05CH11231; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Frontiers in Chemistry
Additional Journal Information:
Journal Name: Frontiers in Chemistry Journal Volume: 6; Journal ID: ISSN 2296-2646
Publisher:
Frontiers Media SA
Country of Publication:
Switzerland
Language:
English
Subject:
36 MATERIALS SCIENCE; zirconium tungstate; EXAFS; DFT; FEFF9; Debye-Waller factors

Citation Formats

Vila, Fernando D., Spencer, John W., Kas, Joshua J., Rehr, John J., and Bridges, Frank. Extended X-Ray Absorption Fine Structure of ZrW2O8: Theory vs. Experiment. Switzerland: N. p., 2018. Web. doi:10.3389/fchem.2018.00356.
Vila, Fernando D., Spencer, John W., Kas, Joshua J., Rehr, John J., & Bridges, Frank. Extended X-Ray Absorption Fine Structure of ZrW2O8: Theory vs. Experiment. Switzerland. doi:10.3389/fchem.2018.00356.
Vila, Fernando D., Spencer, John W., Kas, Joshua J., Rehr, John J., and Bridges, Frank. Thu . "Extended X-Ray Absorption Fine Structure of ZrW2O8: Theory vs. Experiment". Switzerland. doi:10.3389/fchem.2018.00356.
@article{osti_1466058,
title = {Extended X-Ray Absorption Fine Structure of ZrW2O8: Theory vs. Experiment},
author = {Vila, Fernando D. and Spencer, John W. and Kas, Joshua J. and Rehr, John J. and Bridges, Frank},
abstractNote = {Extended x-ray absorption fine structure (EXAFS) is well-suited for investigations of structure and disorder of complex materials. Recently, experimental measurements and analysis of EXAFS have been carried out to elucidate the mechanisms responsible for the negative thermal expansion (NTE) in zirconium tungstate (ZrW2O8). In contrast to previous work suggesting that transverse O-displacements are largely responsible, the EXAFS analysis suggested that correlated rotations and translations of octahedra and tetrahedra within the structure are a major source. In an effort to resolve this controversy, we have carried out ab initio calculations of the structure, lattice vibrations, and EXAFS of ZrW2O8 based on real-space multiple-scattering calculations using the FEFF9 code and auxiliary calculations of structure and Debye-Waller factors. We find that the theoretical simulations are consistent with observed EXAFS, and show that both of the above mechanisms contribute to the dynamical structure of ZrW2O8.},
doi = {10.3389/fchem.2018.00356},
journal = {Frontiers in Chemistry},
number = ,
volume = 6,
place = {Switzerland},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.3389/fchem.2018.00356

Citation Metrics:
Cited by: 1 work
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Figures / Tables:

FIGURE 1 FIGURE 1: | Portion of the unit cell showing the two possible WO4–ZrO6 linkages in ZrW2O8, with Zr (magenta), W1 (blue) and W2 (green), O1 (yellow), O2 (red), O3 (orange), O4 (black). W1, O1, and W2, O2 are the atoms that form Zr-O-W linkages with bridging angles of 155° andmore » 173°, respectively, while the O3 and O4 atoms are only weakly linked (Table 1). [111] denotes the body diagonal direction of the unit cell.« less

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Works referenced in this record:

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