Crystal-Like Atomic Arrangement and Optical Properties of 25La2O3-75MoO3 Binary Glasses Composed of Isolated MoO42.

Transparent and brown La2O3-MoO3 binary glasses were prepared in bulk form using a levitation technique. The glass-forming range was limited, with the primary composition being approximately 25 mol % La2O3. The 25La2O3-75MoO3 glass exhibited a clear crystallization at 546 °C, while determining its glass transition temperature was difficult. Notably, despite its amorphous nature, the glass possessed a density and packing density comparable to those of crystalline La2Mo3O12. X-ray absorption fine structure and Raman scattering analyses revealed that the glass structure closely resembles La2Mo3O12 due to the presence of isolated MoO42- units, whereas disordered atomic arrangement around La atoms was confirmed. The glass demonstrated transparency ranging from 378 to 5500 nm, and the refractive index at 1.0 µm was estimated to be 2.0. The optical bandgap energy was 3.46 eV, which was slightly smaller than that of La2Mo3O12. Additionally, the glass displayed a transparent region ranging from 6.5 to 8.0 µm. This occurrence results from the decreased diversity of MoOn units and connectivity of Mo-O-Mo, which resulted in the reduced overlap of multiphonon absorption. This glass formation, with its departure from conventional glass-forming rules, resulted in distinctive glasses with crystal-like atomic arrangements.

Cascade Charge Transitions of Unusually High and Mixed Valence Fe3.5+ in the A-Site Layer-Ordered Double Perovskite SmBaFe2O6.

The A-site layer-ordered double perovskite SmBaFe2O6 was obtained by topochemical of oxidizing A-site layer-ordered SmBaFe2O5 in ozone at a low temperature. The compound contained unusually high and mixed valence Fe3.5+ and was found to show cascade charge transitions, described as SmBaFe3.5+2O6 → SmBa(Fe3+Fe4+)O6 → SmBa(Fe3+Fe(4-δ)+0.5Fe(4+δ)+0.5)O6 → SmBa(Fe3+1.5Fe5+0.5)O6, to relieve its electronic instability. The first Verwey-like charge-order transition occurred at 340 K and was accompanied by a significant structural change and a sudden increase in magnetic susceptibility. The following transition was the charge disproportionation of metastable Fe4+ to Fe3+ and Fe5+, and each of the spins resulted in the antiferromagnetic ground state. The most plausible charge-ordered patterns are proposed based on the electrostatic lattice energy calculations.

LiNbO3 -Type Polar Antiferromagnet InVO3 Synthesized under High-Pressure Conditions.

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 74 µC cm-2 . Antiferromagnetic coupling of V3+ magnetic moments and a cooperative magnetic ground state below about 10 K coupled with a polar structure suggest an intriguing ground state of the novel LiNbO3 -type high-pressure InVO3 structure.

Giant multiple caloric effects in charge transition ferrimagnet.

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.