Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion
Abstract
Floppy networks (FNs) provide valuable insight into the origin of anomalous mechanical and thermal properties in soft matter systems, from polymers, rubber, and biomolecules to glasses and granular materials. Here, we use the same FN concept to construct a quantitative microscopic theory of empty perovskites, a family of crystals with ReO3 structure, which exhibit a number of unusual properties. One remarkable example is ScF3, which shows a near-zero-temperature structural instability and large negative thermal expansion (NTE). Furthermore, we trace these effects to an FN-like crystalline architecture formed by strong nearest-neighbor bonds, which is stabilized by net electrostatic repulsion that plays a role similar to osmotic pressure in polymeric gels. NTE in these crystalline solids, which we conceptualize as Coulomb floppy networks, emerges from the tension effect of Coulomb repulsion combined with the FN's entropic elasticity and has the same physical origin as in gels and rubber. Our theory provides an accurate, quantitative description of phonons, thermal expansion, compressibility, and structural phase diagram, all in excellent agreement with experiments. The entropic stabilization of critical soft modes, which play only a secondary role in NTE, explains the observed phase diagram. Significant entropic elasticity resolves the puzzle of a marked, ≈50% discrepancy betweenmore »
- Authors:
-
[1];
[2]
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1782554
- Report Number(s):
- BNL-221385-2021-JAAM
Journal ID: ISSN 2469-9950; TRN: US2210016
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review. B
- Additional Journal Information:
- Journal Volume: 103; Journal Issue: 13; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; crystal phenomena; crystal structure; entropy; lattice dynamics; optical phonons; phase diagrams; phase transitions; phonons; structural properties; thermal expansion; thermal properties; thermoelasticity
Citation Formats
Tkachenko, Alexei V., and Zaliznyak, Igor A. Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion. United States: N. p., 2021.
Web. doi:10.1103/physrevb.103.134106.
Tkachenko, Alexei V., & Zaliznyak, Igor A. Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion. United States. https://doi.org/10.1103/physrevb.103.134106
Tkachenko, Alexei V., and Zaliznyak, Igor A. Mon .
"Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion". United States. https://doi.org/10.1103/physrevb.103.134106. https://www.osti.gov/servlets/purl/1782554.
@article{osti_1782554,
title = {Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion},
author = {Tkachenko, Alexei V. and Zaliznyak, Igor A.},
abstractNote = {Floppy networks (FNs) provide valuable insight into the origin of anomalous mechanical and thermal properties in soft matter systems, from polymers, rubber, and biomolecules to glasses and granular materials. Here, we use the same FN concept to construct a quantitative microscopic theory of empty perovskites, a family of crystals with ReO3 structure, which exhibit a number of unusual properties. One remarkable example is ScF3, which shows a near-zero-temperature structural instability and large negative thermal expansion (NTE). Furthermore, we trace these effects to an FN-like crystalline architecture formed by strong nearest-neighbor bonds, which is stabilized by net electrostatic repulsion that plays a role similar to osmotic pressure in polymeric gels. NTE in these crystalline solids, which we conceptualize as Coulomb floppy networks, emerges from the tension effect of Coulomb repulsion combined with the FN's entropic elasticity and has the same physical origin as in gels and rubber. Our theory provides an accurate, quantitative description of phonons, thermal expansion, compressibility, and structural phase diagram, all in excellent agreement with experiments. The entropic stabilization of critical soft modes, which play only a secondary role in NTE, explains the observed phase diagram. Significant entropic elasticity resolves the puzzle of a marked, ≈50% discrepancy between the experimentally observed bulk modulus and ab initio calculations. The Coulomb FN approach is potentially applicable to other important materials with markedly covalent bonds, from perovskite oxides to iron chalcogenides, whose anomalous vibrational and structural properties are still poorly understood.},
doi = {10.1103/physrevb.103.134106},
journal = {Physical Review. B},
number = 13,
volume = 103,
place = {United States},
year = {Mon Apr 12 00:00:00 EDT 2021},
month = {Mon Apr 12 00:00:00 EDT 2021}
}
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