Skip to content Skip to navigation
University of Warwick
  • Study
  • |
  • Research
  • |
  • Business
  • |
  • Alumni
  • |
  • News
  • |
  • About

University of Warwick
Publications service & WRAP

Highlight your research

  • WRAP
    • Home
    • Search WRAP
    • Browse by Warwick Author
    • Browse WRAP by Year
    • Browse WRAP by Subject
    • Browse WRAP by Department
    • Browse WRAP by Funder
    • Browse Theses by Department
  • Publications Service
    • Home
    • Search Publications Service
    • Browse by Warwick Author
    • Browse Publications service by Year
    • Browse Publications service by Subject
    • Browse Publications service by Department
    • Browse Publications service by Funder
  • Help & Advice
University of Warwick

The Library

  • Login
  • Admin

First principles calculation of a large variation in dielectric tensor through the spin crossover in the CsFe[Cr(CN)6] Prussian blue analogue

Tools
- Tools
+ Tools

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

[img]
Preview
PDF
WRAP_CsFeCrC6N6_dielectric_final_withrefs_rev6.pdf - Accepted Version - Requires a PDF viewer.

Download (5Mb) | Preview
[img]
Preview
PDF
WRAP_Supplementary_Material_Rev3.pdf - Supplemental Material - Requires a PDF viewer.

Download (652Kb) | Preview
Official URL: http://dx.doi.org/10.1063/1.4869864

Request Changes to record.

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
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:
DateEvent
14 April 2014Published
9 April 2014Available
18 March 2014Accepted
13 January 2014Submitted
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

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)

Request changes or add full text files to a record

Repository staff actions (login required)

View Item View Item

Downloads

Downloads per month over past year

View more statistics

twitter

Email us: wrap@warwick.ac.uk
Contact Details
About Us