Negative Hydration Expansion in 
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: Microscopic Mechanism, Spaghetti Dynamics, and Negative Thermal Expansion

Baise, Mia; Maffettone, Phillip M.; Trousselet, Fabien; Funnell, Nicholas P.; Coudert, François‐Xavier; Goodwin, Andrew L.

doi:10.1103/physrevlett.120.265501

Cited by 30 publications

(24 citation statements)

References 55 publications

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“…The rigidity constraints could allow chiral motions of the Zr atoms and of the non-bridging O atoms on the WO 4 tetrahedra. For example, a revolution of a terminal O atom would bring it closer in turn to each of the three equivalent positions where it could form a W-O-W bond [55]. As the terminal O atoms are permitted by network topology and crystallographic symmetry to undergo chiral revolutions, it would not be surprising to find such modes with the methods used here.…”

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confidence: 99%

“…The chiral modes found in α-BiB 3 O 6 are distinct from the RUMs which have been used successfully to understand NTE in some materials [10]. However, the RUM model has been found to not apply to many NTE materials, either because of overconstrained coordination polyhedra [53], or because the polyhedra simply are not rigid [54,55]. In materials where the RUM model fails, the origins of NTE often remain incompletely understood, and it is possible that, for chiral systems, calculations of mode circular polarizations could bring additional clarity.…”

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confidence: 99%

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Anomalous thermal expansion and chiral phonons in BiB3O6

Romao

2019

Phys. Rev. B

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The origins of anomalous thermal expansion in the chiral monoclinic solid α-BiB3O6 have been studied through ab initio calculations. Positive and negative axial thermal expansion are shown to be driven by librations of borate units, elastic anisotropy, and most notably by chiral acoustic phonons involving elliptical revolutions of bismuth atoms. The chirality of the lattice gives rise to these modes by allowing the transverse acoustic branches to have opposite circular polarizations, only one of which couples strongly to the lattice strains. These results further understanding of relationships between crystallographic symmetry and physical properties.The monoclinic α phase of bismuth borate (BiB 3 O 6 ), in addition to having promising applications in nonlinear optics [1,2] and quantum computing [3,4], possesses the unusual physical properties of uniaxial negative thermal expansion (NTE) [5,6] and negative linear compressibility (NLC) [7,8] (Fig. 1). The chiral C2 space group adopted by α-BiB 3 O 6 [6] has unusually low symmetry for an NTE material [9, 10], or indeed more generally for an inorganic solid. The chirality of α-BiB 3 O 6 permits it to have chiral phonons, i.e., phonons with a circular polarization and pseudoangular momentum [11][12][13]. Phonon chirality has been shown to affect the anharmonic properties of phonons through the phonon Hall effect [11], and through modification of symmetry constraints for scattering [14], but these previous studies were limited to 1D and 2D materials. The effects of phonon chirality in a 3D crystal are studied here through their relationship to the related anharmonic property of thermal expansion [15].The thermal expansion of α-BiB 3 O 6 is highly anisotropic, with large NTE along a and large positive thermal expansion along b [5,6]. Such behaviour is characteristic of flexible framework materials, i.e., materials which have a mixture of compliant and stiff directions. Indeed, α-BiB 3 O 6 is also very elastically anisotropic: in the ac plane the ratio of Young's moduli between the stiffest and most compliant direction (Y max /Y min ) is 25 (Fig. 1, top); in the ab plane Y max /Y min = 15 (Fig. 1, bottom) [5]. By these standards, α-BiB 3 O 6 is an extraordinarily flexible inorganic material; it can be compared to the colossal NTE material Ag 3 [Co(CN) 6 ], for which Y max /Y min = 6.0 [16,17], and to ZnAu 2 (CN) 4 , which exhibits extreme NLC and has Y max /Y min = 3.8 [18].Axial NTE has been studied extensively in the tetragonal, orthorhombic, and hexagonal crystal families due to the appearance of anomalously large-magnitude thermal expansion [17], connections with ferroelectricity [19,20], and the use of chemical control to achieve zero thermal expansion [21]. However, NTE is extremely rare in monoclinic and triclinic crystals [9,10]. Outside of α-BiB 3 O 6 , c a a b c FIG. 1. At left, the structure of α-BiB3O6 is shown in the ac plane (top) and the ab plane (bottom), with bismuth atoms coloured in magenta and borate units coloured in green [6]. At right, the indica...

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Anomalous thermal expansion and chiral phonons in BiB3O6

Romao

2019

Phys. Rev. B

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“…However in some cases, even small molecules can ingress in formally nonporous dense framework materials. Recently, Goodwin 20% more dense [79]. Examination of the correlated translation, rotation and distortion of ZrO 6 /WO 4 study identified "spaghetti-like" displacements of a W O W network which are responsible for NHE in this material.…”

Section: Adsorption-induced Contractionmentioning

confidence: 87%

Meta-MOFs: Framework Materials with Anomalous Behavior

Coudert¹,

Evans²

2018

Preprint

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As the number of framework materials known and characterized in the literature grows, it becomes apparent that they can carry properties rarely encountered in more conventional, dense inorganic materials. Among these materials with unusual physical or chemical properties are the ubiquitous metal–organic frameworks, covalent organic frameworks, dense coordination polymers, and molecular frameworks. Many can respond to stimulation by displaying structural responses and changes in properties that range from counter-intuitive to thermodynamically forbidden. In that, they share large similarities with metamaterials, which are engineered to generate properties not found in “normal” materials. We review here the surprising behavior of these meta-MOFs, that display properties “beyond” (μετά) the boundaries of common crystalline materials.<br>

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“…Recently, Goodwin and coworkers described negative hydration expansion (NHE) in zirconium tungstate, Zr 2 W 2 O 8 . Though nonporous, this structure can be reversibly hydrated to Zr 2 W 2 O 8 · H 2 O, transforming to a disordered phase that is 20% more dense [91]. Examination of the correlated translation, rotation and distortion of ZrO 6 /WO 4 study identified "spaghetti-like" displacements of a W−O−W network which are responsible for NHE in this material.…”

Section: Adsorption-induced Contractionmentioning

confidence: 91%

Nanoscale Metamaterials: Meta-MOFs and Framework Materials with Anomalous Behavior

Coudert

Evans²

2019

Preprint

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As the number of framework materials known and characterized in the literature grows, it becomes apparent that they can carry properties rarely encountered in more conventional, dense inorganic materials. Among these materials with unusual physical or chemical properties are the ubiquitous metal-organic frameworks, covalent organic frameworks, dense coordination polymers, and molecular frameworks. Many can respond to stimulation by displaying structural responses and changes in properties that range from counter-intuitive to thermodynamically forbidden. In that, they share large similarities with metamaterials, which are engineered to generate properties not found in "normal" materials. We review here the surprising behavior of these meta-MOFs and other framework materials that display properties "beyond" (μετά) the boundaries of common crystalline materials.

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Negative Hydration Expansion in ZrW2O8 : Microscopic Mechanism, Spaghetti Dynamics, and Negative Thermal Expansion

Cited by 30 publications

References 55 publications

Anomalous thermal expansion and chiral phonons in BiB3O6

Anomalous thermal expansion and chiral phonons in BiB3O6

Meta-MOFs: Framework Materials with Anomalous Behavior

Nanoscale Metamaterials: Meta-MOFs and Framework Materials with Anomalous Behavior

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