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First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN)6] Prussian blue analogue
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Middlemiss, Derek S. and Deeth, Robert J. (2014) First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN)6] Prussian blue analogue. Journal of Chemical Physics, Volume 140 (Number 14). Article number 144503. doi:10.1063/1.4869864
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Official URL: http://dx.doi.org/10.1063/1.4869864
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.
| Item Type: | Journal Article | ||||||||||
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| Subjects: | Q Science > QC Physics | ||||||||||
| Divisions: | Faculty of Science > Chemistry | ||||||||||
| Library of Congress Subject Headings (LCSH): | Dielectrics, Density functionals | ||||||||||
| Journal or Publication Title: | Journal of Chemical Physics | ||||||||||
| Publisher: | American Institute of Physics | ||||||||||
| ISSN: | 0021-9606 | ||||||||||
| Official Date: | 14 April 2014 | ||||||||||
| Dates: |
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| Date of first compliant deposit: | 27 December 2015 | ||||||||||
| Volume: | Volume 140 | ||||||||||
| Number: | Number 14 | ||||||||||
| Article Number: | Article number 144503 | ||||||||||
| DOI: | 10.1063/1.4869864 | ||||||||||
| Status: | Peer Reviewed | ||||||||||
| Publication Status: | Published | ||||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||||
| Description: | Includes supplementary material |
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| Funder: | Engineering and Physical Sciences Research Council (EPSRC), United States. Department of Energy. Office of Basic Energy Sciences (OBES) | ||||||||||
| Grant number: | EP/K012940/1 (EPSRC), DE-AC02-98CH10886 (OBES) |
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