In:
The Journal of Chemical Physics, AIP Publishing, Vol. 140, No. 14 ( 2014-04-14)
Abstract:
The dielectric response of spin-crossover (SCO) materials is a key property facilitating their use in next-generation information processing technologies. Solid state hybrid density functional theory calculations show that the temperature-induced and strongly hysteretic SCO transition in the Cs+Fe2+[Cr3+(CN−)6] Prussian blue analogue (PBA) is associated with a large change (Δ) in both the static, Δɛ0(HS − LS), and high frequency, Δɛ∞(HS − LS) dielectric constants. The SCO-induced variation in CsFe[Cr(CN)6] is significantly greater than the experimental Δɛ values observed previously in other SCO materials. The phonon contribution, Δɛphon(HS − LS), determined within a lattice dynamics approach, dominates over the clamped nuclei term, Δɛ∞(HS − LS), and is in turn dominated by the low-frequency translational motions of Cs+ cations within the cubic voids of the Fe[Cr(CN)6]− framework. The Cs+ translational modes couple strongly to the large unit cell volume change occurring through the SCO transition. PBAs and associated metal-organic frameworks emerge as a potentially fruitful class of materials in which to search for SCO transitions associated with large changes in dielectric response and other macroscopic properties.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
2014
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
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