The origin of uniaxial negative thermal expansion in layered perovskites
File(s)
Supporting information
Accepted version
Author(s)
Ablitt, C
Craddock, S
Senn, MS
Mostofi, AA
Bristowe, NC
Type
Journal Article
Abstract
Why is it that ABO3 perovskites generally do not exhibit negative thermal expansion (NTE) over a wide temperature range, whereas layered perovskites of the same chemical family often do? It is generally accepted that there are two key ingredients that determine the extent of NTE: the presence of soft phonon modes that drive contraction (have negative Grüneisen parameters); and anisotropic elastic compliance that predisposes the material to the deformations required for NTE along a specific axis. This difference in thermal expansion properties is surprising since both ABO3 and layered perovskites often possess these ingredients in equal measure in their high-symmetry phases. Using first principles calculations and symmetry analysis, we show that in layered perovskites there is a significant enhancement of elastic anisotropy due to symmetry breaking that results from the combined effect of layering and condensed rotations of oxygen octahedra. This feature, unique to layered perovskites of certain symmetry, is what allows uniaxial NTE to persist over a large temperature range. This fundamental insight means that symmetry and the elastic tensor can be used as descriptors in high-throughput screening and to direct materials design.
Date Issued
2017-10-16
Date Acceptance
2017-08-08
Citation
npj Computational Materials, 2017, 3 (10)
ISSN
2057-3960
Publisher
Nature Publishing Group
Journal / Book Title
npj Computational Materials
Volume
3
Issue
10
Copyright Statement
This article is licensed under a Creative Commons
Attribution 4.0 International License, which permits use, sharing,
adaptation, distribution and reproduction in any medium or format, as long as you give
appropriate credit to the original author(s) and the source, provide a link to the Creative
Commons license, and indicate if changes were made. The images or other third party
material in this article are included in the article’s Creative Commons license, unless
indicated otherwise in a credit line to the material. If material is not included in the
article’s Creative Commons license and your intended use is not permitted by statutory
regulation or exceeds the permitted use, you will need to obtain permission directly
from the copyright holder. To view a copy of this license, visit http://creativecommons.
org/licenses/by/4.0/.
© The Author(s) 2017
Attribution 4.0 International License, which permits use, sharing,
adaptation, distribution and reproduction in any medium or format, as long as you give
appropriate credit to the original author(s) and the source, provide a link to the Creative
Commons license, and indicate if changes were made. The images or other third party
material in this article are included in the article’s Creative Commons license, unless
indicated otherwise in a credit line to the material. If material is not included in the
article’s Creative Commons license and your intended use is not permitted by statutory
regulation or exceeds the permitted use, you will need to obtain permission directly
from the copyright holder. To view a copy of this license, visit http://creativecommons.
org/licenses/by/4.0/.
© The Author(s) 2017
License URL
Sponsor
Engineering and Physical Sciences Research Council
Grant Number
EP/L015579/1
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Materials Science, Multidisciplinary
Chemistry
Materials Science
RIGID UNIT MODES
X-RAY
MOLECULAR-DYNAMICS
CRYSTAL-STRUCTURES
TEMPERATURE
BEHAVIOR
DIFFRACTION
TRANSITIONS
OXIDE
Publication Status
Published
Article Number
ARTN 44
Date Publish Online
2017-08-17