RESUMO
CdMnO3 had not been previously reported and was a missing piece in the A2+Mn4+O3 series. We succeeded in synthesizing this compound by a high-pressure method and confirmed that it is crystallized in a distorted perovskite structure with a Cd2+Mn4+O3 charge configuration. The obtained insulating CdMnO3 exhibits an antiferromagnetic transition at about 86 K. First-principles calculations revealed that the Mn4+ (t2g3) spins form a C-type antiferromagnetic structure, which is in sharp contrast to the G-type antiferromagnetism in the isostructural and isoelectronic CaMnO3. Significant overlap of the Mn-3d and O(2)-2p orbitals produces distorted octahedra with a large Mn-O(1)-Mn tilt and induces antiferromagnetic couplings in the ac plane and the ferromagnetic couplings along the b axis.
RESUMO
The ambient pressure cation disordered InVO3 bixbyite has been predicted to form a GdFeO3 -type perovskite phase under high pressure and high temperature. Contrary to the expectation, InVO3 was found to crystallize in the polar LiNbO3 -type structure with a calculated spontaneous polarization as large as 74â µC cm-2 . Antiferromagnetic coupling of V3+ magnetic moments and a cooperative magnetic ground state below about 10â K coupled with a polar structure suggest an intriguing ground state of the novel LiNbO3 -type high-pressure InVO3 structure.
RESUMO
Two hexagonal-perovskite-structure oxides, 21R Ba7Fe5Ge2O20 and 12H Ba6Fe3Ge3O17, were obtained by synthesis with a high-pressure and high-temperature technique. The Fe-containing hexagonal-perovskite-structure units are sandwiched by nonmagnetic GeO4 tetrahedral layers in the structures, and thus both compounds show two-dimensional ferrimagnetic behaviors due to intra- and interunit magnetic interactions. 21R Ba7Fe5Ge2O20 has the ionic formula Ba7Fe123+Fe24+Fe324+Ge424+O20 at room temperature, and unusually high valence Fe4+ in the trimers undergoes charge disproportionation, Fe24+ + 2Fe34+ â Fe2(4+2δ)+ + 2Fe3(4-δ)+, at low temperatures. In contrast, 12H Ba6Fe3Ge3O17 with ionic formula Ba6Fe123+(Fe20.54+Ge20.54+)2Ge324+O17 does not show a charge transition.
RESUMO
BaFe xNi1- xO3 with end members of BaNiO3 ( x = 0) and BaFeO3 ( x = 1), which, respectively, adopt the 2H and 6H hexagonal perovskite structures, were synthesized, and their crystal structures were investigated. A new single phase, Ba4Fe3NiO12 ( x = 0.75), that adopts the 12R perovskite structure with the space group R3Ì m ( a = 5.66564(7) Å and c = 27.8416(3) Å), was found to be stabilized. Mössbauer spectroscopy results and structure analysis using synchrotron and neutron powder diffraction data revealed that nominal Fe3+ occupies the corner-sharing octahedral site while the unusually high valence Fe4+ and Ni4+ occupy the face-sharing octahedral sites in the trimers, giving a charge formula of Ba4Fe3+Fe4+2Ni4+O11.5. The magnetic properties of the compound are also discussed.
RESUMO
Caloric effects of solids can provide us with innovative refrigeration systems more efficient and environment-friendly than the widely-used conventional vapor-compression cooling systems. Exploring novel caloric materials is challenging but critically important in developing future technologies. Here we discovered that the quadruple perovskite structure ferrimagnet BiCu3Cr4O12 shows large multiple caloric effects at the first-order charge transition occurring around 190 K. Large latent heat and the corresponding isothermal entropy change, 28.2 J K-1 kg-1, can be utilized by applying both magnetic fields (a magnetocaloric effect) and pressure (a barocaloric effect). Adiabatic temperature changes reach 3.9 K for the 50 kOe magnetic field and 4.8 K for the 4.9 kbar pressure, and thus highly efficient thermal controls are achieved in multiple ways.