Structures and negative thermal expansion properties of the one-dimensional cyanides, CuCN, AgCN and AuCN

Hibble, Simon J.; Wood, Glenn B.; Bilbé, Edward J.; Pohl, Alexander; Tucker, Matthew G.; Hannon, Alex C.; Chippindale, Ann M.

doi:10.1524/zkri.2010.1314

Cited by 36 publications

(73 citation statements)

References 13 publications

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“…, Ref. [49,53]), and is presumably tempered here somewhat relative to that system by the increased strength of Co −C III vs Cu −C I bonds [47]. One consequence of the negative value of α r is that the volume coefficient of thermal expansion of Cu 3 [Co(CN) 6 ] is unusually small for systems in this particular family.…”

Section: Thermal Expansion Behaviourmentioning

confidence: 99%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu 3 [Co(CN) 6 ], which we find to be isostructural to H 3 [Co(CN) 6 ] and the colossal negative thermal expansion material Ag 3 [Co(CN) 6 ]. Using synchrotron X-ray powder diffraction measurements, we find strong positive and negative thermal expansion behaviour respectively perpendicular and parallel to the trigonal crystal axis: α = 25.4(5) MK . These opposing effects collectively result in a volume expansivity α = 7.4(11) MK V −1 that is remarkably small for an anisotropic molecular framework. This thermal response is discussed in the context of the behaviour of the analogous H-and Ag-containing systems. We make use of density-functional theory with many-body dispersion interactions (DFT + MBD) to demonstrate that Cu + …Cu + metallophilic ('cuprophilic') interactions are significantly weaker in Cu 3 [Co(CN) 6 ] than Ag + …Ag + interactions in Ag 3 [Co(CN) 6 ], but that this lowering of energy scale counterintuitively translates to a more moderate-rather than enhanced-degree of structural flexibility. The same conclusion is drawn from consideration of a simple GULP model, which we also present here. Our results demonstrate that strong interactions can actually be exploited in the design of ultra-responsive materials if those interactions are set up to act in tension.

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Section: Thermal Expansion Behaviourmentioning

confidence: 99%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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“…The phonon spectra have been calculated in partially relaxed configuration. In partially relaxed only atomic coordinates are relaxed at fixed lattice parameter obtained from neutron diffraction data at 10 K and 310 K 39,42,44,56 .…”

Section: Computational Detailsmentioning

confidence: 99%

“…The crystal structure of all three metal cyanides is known to show C/N disorder 39 We have also calculated the phonon dispersion (Fig 5) The C 66 elastic constant in all three compounds is very small. All these suggest that CuCN and AgCN are close to instability in plane against shear strain.…”

Section: B Calculated Phonon Spectra and Elastic Constantsmentioning

confidence: 99%

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Lattice dynamics and thermal expansion behavior in the metal cyanidesMCN(M=Cu, Ag, Au): Neutron inelastic scattering and first-principles calculations

et al. 2016

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We report measurement of temperature dependence of phonon spectra in quasi one-dimensional metal cyanides MCN (M=Cu, Ag and Au). Ab-initio lattice dynamics calculations have been performed to interpret the phonon-spectra as well as to understand the anamolous thermal expansion behavior in these compounds. We bring out the differences in the phonon mode behavior to explain the differences in the thermal expansion behavior among the three compounds. The chain-sliding modes are found to contribute maximum to the negative thermal expansion along "c" axis in the Cu-and Ag-compounds, while the same modes contribute to positive thermal expansion in the Au-compound. Several low energy transverse modes lead to positive thermal expansion along "a" and "b" axis in all the compounds.The calculated elastic constants and Born effective charges are correlated with the difference in nature of bonding among these metal cyanides.

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“…Including the Bragg profile ensures that the refined model is consistent with both the three-dimensional average structure and the local structure revealed by the total-scattering data. Figure 3 shows part of an AgCN atomic configuration obtained by using RMCProfile (13) and the same configuration folded back onto the average crystallographic unit cell. The chains of atoms move up and down the c axis and have a wavelike shape.…”

Section: Rmcprofile: Reverse Monte Carlo For Polycrystalline Systemsmentioning

confidence: 99%

New Insights into Complex Materials Using Reverse Monte Carlo Modeling

Playford

Owen

Levin

et al. 2014

Annu. Rev. Mater. Res.

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Local structure and disorder in crystalline materials are increasingly recognized as the key to understanding their functional properties. From negative thermal expansion to dielectric response to thermoelectric properties to ionic conductivity, a clear picture of the local atomic arrangements is essential for understanding these phenomena and developing new practical systems. The combination of total scattering and reverse Monte Carlo (RMC) modeling can provide an unprecedented level of structural detail. In this article, we briefly introduce the method and present a short overview of the scientific areas in which RMC has provided important new insights. Finally, we discuss how the RMC algorithm can be used to combine inputs from multiple experimental techniques, thus moving toward a complex modeling paradigm and helping us to fully understand complex functional materials. 429 Annu. Rev. Mater. Res. 2014.44:429-449. Downloaded from www.annualreviews.org by Dalhousie University on 07/08/14. For personal use only.

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Structures and negative thermal expansion properties of the one-dimensional cyanides, CuCN, AgCN and AuCN

Cited by 36 publications

References 13 publications

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Lattice dynamics and thermal expansion behavior in the metal cyanidesMCN(M=Cu, Ag, Au): Neutron inelastic scattering and first-principles calculations

New Insights into Complex Materials Using Reverse Monte Carlo Modeling

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