Phase transitions that occur in materials, driven, for instance, by changes in temperature or pressure, can dramatically change the materials' properties. Discovering new types of transitions and understanding their mechanisms is important not only from a fundamental perspective, but also for practical applications. Here we investigate a recently discovered Fe4O5 that adopts an orthorhombic CaFe3O5-type crystal structure that features linear chains of Fe ions. On cooling below ∼150 K, Fe4O5 undergoes an unusual charge-ordering transition that involves competing dimeric and trimeric ordering within the chains of Fe ions. This transition is concurrent with a significant increase in electrical resistivity. Magnetic-susceptibility measurements and neutron diffraction establish the formation of a collinear antiferromagnetic order above room temperature and a spin canting at 85 K that gives rise to spontaneous magnetization. We discuss possible mechanisms of this transition and compare it with the trimeronic charge ordering observed in magnetite below the Verwey transition temperature.
The crystal and magnetic structures of BiMnO 3 were studied at high pressures up to 10 GPa by means of neutron diffraction in the temperature range 2-300 K. Three structural modifications, two monoclinic and one orthorhombic were found to exist in the pressure range studied and their structural parameters were determined. A suppression of the initial ferromagnetic state and formation of a new antiferromagnetic state with a propagation vector ͑1/2 1/2 1/2͒ was observed at P ϳ 1 GPa, accompanied with the monoclinic-monoclinic structural transformation. Possible mechanisms of the pressure-induced magnetic transition and origin of magnetoelectric phenomena in BiMnO 3 are discussed.
Abstract. Measurements of spin-lattice relaxation time T 1 for resorcinol have been made by the proton NMR technique using the saturation method in the temperature range 280 -380 K and pressure up to 800 MPa. The pressure-induced -β transition evolved through two phase coexistence range was observed. The crystal structure and vibrational spectra of the resorcinol have also been studied by means of X-ray diffraction and Raman spectroscopy at pressures up to 19 GPa in temperature range 290 -380 К. In experiments with a rapid pressurization rate, suppression of α-β polymorphic transition in resorcinol occurs. In experiments with a slow pressurization rate, two structural phase transitions, between orthorhombic α and β phases at P = 0.4 GPa and from β to another orthorhombic phase at P=5.6 GPa, were observed. At pressures above 12.5 GPa, a gradual transformation to the amorphous phase was revealed. The lattice parameters, unit cell volumes and vibration modes as functions of pressure and temperature were obtained for the different polymorphic modifications of resorcinol.
The magnetic structures of hexagonal manganites
YMnO3
and LuMnO3
have been studied by powder neutron diffraction up to 6 GPa in the temperature range
10–295 K. At ambient pressure, a triangular antiferromagnetic (AFM) state of a
Γ1 irreducible representation
is stable below TN = 70 K
in YMnO3. Upon
the application of high pressure, a spin reorientation is induced and the triangular AFM structure evolves
from Γ1
to Γ1+Γ2
representations. On the other hand, in
LuMnO3 the triangular AFM
state of a Γ2 irreducible
representation with TN≈90 K
remains stable over the entire pressure range investigated. The
ordered magnetic moment values decrease under pressure with
dM/dP = −0.35 μB GPa−1 in
YMnO3
and −0.08 μB GPa−1
in LuMnO3. Simultaneously, a considerable increase in diffuse scattering intensity was found in
YMnO3, while it was much
less pronounced for LuMnO3. Both features indicate the enhancement of spin fluctuations due to geometrical
frustration effects and an increase in the volume fraction of the spin-liquid state
coexisting with the ordered AFM phase. The characteristic spin correlation length
is weakly affected by pressure. The relationship between the pressure-induced
behaviour of magnetic structure and the structural characteristics of the
quasi-two-dimensional (2D) triangular network formed by Mn and O ions in hexagonal
RMnO3
is analysed.
The structural and magnetic properties of multiferroic CuO have been studied by means of neutron and x-ray powder diffraction at pressures up to 11 and 38 GPa, respectively, and by first-principles theoretical calculations. Anomalous lattice compression is observed, with enlargement of the lattice parameter a, reaching a maximum at P = 13 GPa, followed by its reduction at higher pressures. The lattice distortion of the monoclinic structure at high pressures is accompanied by a progressive change of the oxygen coordination around Cu atoms from the square fourfold towards the octahedral sixfold coordination. The pressure-induced evolution of the structural properties and electronic structure of CuO was successfully elucidated in the framework of full-electronic density functional theory calculations with range-separated HSE06, and meta-generalized gradient approximation hybrid M06 functionals. The antiferromagnetic (AFM) ground state with a propagation vector q = (0.5,0, − 0.5) remains stable in the studied pressure range. From the obtained structural parameters, the pressure dependencies of the principal superexchange magnetic interactions were analyzed, and the pressure behavior of the Néel temperature as well as the magnetic transition temperature from the intermediate incommensurate AFM multiferroic state to the commensurate AFM ground state were evaluated. The estimated upper limit of the Néel temperature at P = 38 GPa is about 260 K, not supporting the previously predicted existence of the multiferroic phase at room temperature and high pressure.
The ABO3 perovskite oxides exhibit a wide range of interesting physical phenomena remaining in the focus of extensive scientific investigations and various industrial applications. In order to form a perovskite structure, the cations occupying the A and B positions in the lattice, as a rule, should be different. Nevertheless, the unique binary perovskite manganite Mn2O3 containing the same element in both A and B positions can be synthesized under high-pressure high-temperature conditions. Here, we show that this material exhibits magnetically driven ferroelectricity and a pronounced magnetoelectric effect at low temperatures. Neutron powder diffraction revealed two intricate antiferromagnetic structures below 100 K, driven by a strong interplay between spin, charge, and orbital degrees of freedom. The peculiar multiferroicity in the Mn2O3 perovskite is ascribed to a combined effect involving several mechanisms. Our work demonstrates the potential of binary perovskite oxides for creating materials with highly promising electric and magnetic properties.
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