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Title: Efficient Calculation of the Negative Thermal Expansion in ZrW2O8

Abstract

We present a study of the origin of the negative thermal expansion (NTE) on ZrW 2O 8 by combining an efficient approach for computing the dynamical matrix with the Lanczos algorithm for generating the phonon density of states in the quasi-harmonic approximation. The simulations show that the NTE arises primarily from the motion of the O-sublattice, and in particular, from the transverse motion of the O atoms in the W–O and W–O–Zr bonds. In the low frequency range these combine to keep the WO 4 tetrahedra rigid and induce internal distortions in the ZrO 6 octahedra. The force constants associated with these distortions become stronger with expansion, resulting in negative Grüneisen parameters and NTE from the low frequency modes that dominate the positive contributions from the high frequency modes. This leads us to propose an anharmonic, two-frequency Einstein model that quantitatively captures the NTE behavior.

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Illinois, Urbana-Champaign, IL (United States) Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1462120
Alternate Identifier(s):
OSTI ID: 1510436
Grant/Contract Number:  
CSGBD Grant No. DE-FG02-03ER15476; FG02-03ER15476; AC02-05CH11231
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:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zirconium tungstate; NTE; DFT; quasi-harmonic approximation; phonon density of states

Citation Formats

Vila, Fernando D., Hayashi, Scott T., and Rehr, John J. Efficient Calculation of the Negative Thermal Expansion in ZrW2O8. Switzerland: N. p., 2018. Web. doi:10.3389/fchem.2018.00296.
Vila, Fernando D., Hayashi, Scott T., & Rehr, John J. Efficient Calculation of the Negative Thermal Expansion in ZrW2O8. Switzerland. doi:10.3389/fchem.2018.00296.
Vila, Fernando D., Hayashi, Scott T., and Rehr, John J. Mon . "Efficient Calculation of the Negative Thermal Expansion in ZrW2O8". Switzerland. doi:10.3389/fchem.2018.00296.
@article{osti_1462120,
title = {Efficient Calculation of the Negative Thermal Expansion in ZrW2O8},
author = {Vila, Fernando D. and Hayashi, Scott T. and Rehr, John J.},
abstractNote = {We present a study of the origin of the negative thermal expansion (NTE) on ZrW2O8 by combining an efficient approach for computing the dynamical matrix with the Lanczos algorithm for generating the phonon density of states in the quasi-harmonic approximation. The simulations show that the NTE arises primarily from the motion of the O-sublattice, and in particular, from the transverse motion of the O atoms in the W–O and W–O–Zr bonds. In the low frequency range these combine to keep the WO4 tetrahedra rigid and induce internal distortions in the ZrO6 octahedra. The force constants associated with these distortions become stronger with expansion, resulting in negative Grüneisen parameters and NTE from the low frequency modes that dominate the positive contributions from the high frequency modes. This leads us to propose an anharmonic, two-frequency Einstein model that quantitatively captures the NTE behavior.},
doi = {10.3389/fchem.2018.00296},
journal = {Frontiers in Chemistry},
number = ,
volume = 6,
place = {Switzerland},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.3389/fchem.2018.00296

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

FIGURE 1 FIGURE 1: | Structure of the ZrW2O8 cell. The cell is composed of four equivalent Zr atoms (magenta), eight W atoms, of type WFF (blue) and WFR (green), and 32 O atoms of type OLS (yellow), OSL (red), OFR (orange) and OFF (black). Examples of the different types of Omore » and W atoms are highlighted, and the coordination tetrahedra and octahedra are also included for clarity. The WFF, WFR, OLS, OSL, OFR, and OFF atoms correspond, respectively, to the W1, W2, O1, O2, O3, and O4 in the traditional notation (Mary et al., 1996).« less

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