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Low-Frequency Phonon Driven Negative Thermal Expansion in Cubic GaFe(CN)6 Prussian Blue Analogues

Journal Article · · Inorganic Chemistry
 [1];  [1];  [2];  [3];  [3];  [3];  [1];  [4];  [4];  [5];  [1];  [1]
  1. Univ. of Science and Technology Beijing, Beijing (China)
  2. Zhengzhou Univ., Zhengzhou (China)
  3. Univ. of Padova, Padova (Italy)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
+ Show Author Affiliations
Here, the understanding of the negative thermal expansion (NTE) mechanism is vital not only for the development of new NTE compounds but also for effectively controlling thermal expansion. Here, we report an interesting isotropic NTE property in cubic GaFe(CN)6 Prussian blue analogues (αl = –3.95 × 10–6 K–1, 100–475 K), which is a new example to understand the complex NTE mechanism. A combined study of synchrotron X-ray diffraction, X-ray total scattering, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations shows that the NTE of GaFe(CN)6 originates from the low-frequency phonons (< ~100 cm–1), which are directly related to the transverse vibrations of the atomic –Ga–N≡C–Fe– chains. Both the Ga–N and Fe–C chemical bonds are much softer to bend than to stretch. The direct evidence that transverse vibrational contribution to the NTE of GaFe(CN)6 is dominated by N, instead of C atoms, is illustrated. It is interesting to find that the polyhedra of GaFe(CN)6 are not rigid, which is a starting assumption in some models describing the NTE properties of other systems. The NTE mechanism can be vividly described by the “guitar-string” effect, which would be the common feature for the NTE property of many open-framework functional materials, such as Prussian blue analogues, oxides, cyanides, metal–organic frameworks, and zeolites.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1472117
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 17 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Perovskite-related ReO3-type structures journal January 2020
Negative thermal expansion in cubic FeFe(CN) 6 Prussian blue analogues journal January 2019
Negative thermal expansion behavior in orthorhombic Sc 2 (MoO 4 ) 3 and Sc 2 (WO 4 ) 3 journal September 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY