Universität zu Köln

Layek, Samar ORCID: 0000-0002-1874-7220, Greenberg, Eran, Chariton, Stella, Bykov, Maxim ORCID: 0000-0003-0248-1728, Bykova, Elena, Trots, Dmytro M., Kurnosov, Alexander, V, Chuvashova, Irina, Ovsyannikov, Sergey, V, Leonov, Ivan and Rozenberg, Gregory Kh (2022). Verwey-Type Charge Ordering and Site-Selective Mott Transition in Fe4O5 under Pressure. J. Am. Chem. Soc., 144 (23). S. 10259 - 10270. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-5126

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Abstract

The metal-insulator transition driven by electronic correlations is one of the most fundamental concepts in condensed matter. In mixed-valence compounds, this transition is often accompanied by charge ordering (CO), resulting in the emergence of complex phases and unusual behaviors. The famous example is the archetypal mixed-valence mineral magnetite, Fe3O4., exhibiting a complex charge-ordering below the Verwey transition, whose nature has been a subject of long-time debates. In our study, using high-resolution X-ray diffraction supplemented by resistance measurements and DFT+DMFT calculations, the electronic, magnetic, and structural properties of recently synthesized mixed-valence Fe4O5 are investigated under pressure to similar to 100 GPa. Our calculations, consistent with experiment, reveal that at ambient conditions Fe4O5 is a narrow-gap insulator characterized by the original Verwey-type CO. Under pressure Fe4O5 undergoes a series of electronic and magnetic-state transitions with an unusual compressional behavior above similar to 50 GPa. A site-dependent collapse of local magnetic moments is followed by the site-selective insulator-to-metal transition at similar to 84 GPa, occurring at the octahedral Fe sites. This phase transition is accompanied by a 2+ to 3+ valence change of the prismatic Fe ions and collapse of CO. We provide a microscopic explanation of the complex charge ordering in Fe4O5 which unifies it with the behavior of two archetypal examples of charge- or bond-ordered materials, magnetite and rare-earth nickelates (RNiO3). We find that at low temperatures the Verwey-type CO competes with the trimeron/dimeron charge ordered states, allowing for pressure/temperature tuning of charge ordering. Summing up the available data, we present the pressure-temperature phase diagram of Fe4O5.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Layek, Samar UNSPECIFIED orcid.org/0000-0002-1874-7220 UNSPECIFIED Greenberg, Eran UNSPECIFIED UNSPECIFIED UNSPECIFIED Chariton, Stella UNSPECIFIED UNSPECIFIED UNSPECIFIED Bykov, Maxim UNSPECIFIED orcid.org/0000-0003-0248-1728 UNSPECIFIED Bykova, Elena UNSPECIFIED UNSPECIFIED UNSPECIFIED Trots, Dmytro M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Kurnosov, Alexander, V UNSPECIFIED UNSPECIFIED UNSPECIFIED Chuvashova, Irina UNSPECIFIED UNSPECIFIED UNSPECIFIED Ovsyannikov, Sergey, V UNSPECIFIED UNSPECIFIED UNSPECIFIED Leonov, Ivan UNSPECIFIED UNSPECIFIED UNSPECIFIED Rozenberg, Gregory Kh UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-693097
DOI:	10.1021/jacs.2c00895
Journal or Publication Title:	J. Am. Chem. Soc.
Volume:	144
Number:	23
Page Range:	S. 10259 - 10270
Date:	2022
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-5126
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language EQUATION-OF-STATE; MAGNETITE FE3O4; RNIO3 R; SPIN; PEROVSKITES; PHYSICS; LIMIT Multiple languages Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/69309