Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion

Tkachenko, Alexei V.; Zaliznyak, Igor A.

doi:10.1103/physrevb.103.134106

Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion

Journal Article · Mon Apr 12 00:00:00 EDT 2021 · Physical Review. B

DOI:https://doi.org/10.1103/physrevb.103.134106· OSTI ID:1782554

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Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1782554

Report Number(s):: BNL--221385-2021-JAAM

Journal Information:: Physical Review. B, Journal Name: Physical Review. B Journal Issue: 13 Vol. 103; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Empty perovskites as Coulomb floppy networks: Entropic elasticity and negative thermal expansion

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