We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd3S4, by electrical transport, X-ray diffraction, time-domain151Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature,TN, increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated withTNis detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to theTNplateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu2+:Eu3+to fully Eu3+at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhancesTN, most likely via enhanced hybridization between the Eu 4fstates and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state. 
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                            High-Pressure Polymorphism in Silver Ferrite Delafossite, AgFeO 2
                        
                    
    
            The delafossites are a class of layered metal oxides that are notable for being able to exhibit optical transparency alongside an in-plane electrical conductivity, making them promising platforms for the development of transparent conductive oxides. Pressure-induced polymorphism offers a direct method for altering the electrical and optical properties in this class, and although the copper delafossites have been studied extensively under pressure, the silver delafossites remain only partially studied. We report two new high-pressure polymorphs of silver ferrite delafossite, AgFeO2, that are stabilized above ∼6 and ∼14 GPa. In situ X-ray diffraction and vibrational spectroscopy measurements are used to examine the structural changes across the two phase transitions. The high-pressure structure between 6 and 14 GPa is assigned as a monoclinic C2/c structure that is analogous to the high-pressure phase reported for AgGaO2. Nuclear resonant forward scattering reveals no change in the spin state or valence state at the Fe3+ site up to 15.3(5) GPa. 
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                            - Award ID(s):
- 2004474
- PAR ID:
- 10525141
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 63
- Issue:
- 21
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 9763 to 9770
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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