Evidence of Strong Orbital-Selective Spin-Orbital-Phonon Coupling in CrVO_{4}.

Coupling of orbital degree of freedom with a spin exchange, i.e., Kugel-Khomskii-type interaction (KK), governs a host of material properties, including colossal magnetoresistance, enhanced magnetoelectric response, and photoinduced high-temperature magnetism. In general, KK-type interactions lead to deviation in experimental observables of coupled Hamiltonian near or below the magnetic transition. Using diffraction and spectroscopy experiments, here we report anomalous changes in lattice parameters, electronic states, spin dynamics, and phonons at four times the Néel transition temperature (T_{N}) in CrVO_{4}. The temperature is significantly higher than other d-orbital compounds such as manganites and vanadates, where effects are limited to near or below T_{N}. The experimental observations are rationalized using first-principles and Green's function-based phonon and spin simulations that show unprecedentedly strong KK-type interactions via a superexchange process and an orbital-selective spin-phonon coupling coefficient at least double the magnitude previously reported for strongly coupled spin-phonon systems. Our results present an opportunity to explore the effect of KK-type interactions and spin-phonon coupling well above T_{N} and possibly bring various properties closer to application, for example, strong room-temperature magnetoelectric coupling.

Equations of State and Crystal Structures of KCaPO4, KSrPO4, and K2Ce(PO4)2 under High Pressure: Discovery of a New Polymorph of KCaPO4.

We have studied by means of angle-dispersive powder synchrotron X-ray diffraction the structural behavior of KCaPO4, SrKPO4, and K2Ce(PO4)2 under high pressure up to 26, 25, and 22 GPa, respectively. For KCaPO4, we have also accurately determined the crystal structure under ambient conditions, which differs from the structure previously reported. Arguments supporting our structural determination will be discussed. We have found that KCaPO4 undergoes a reversible phase transition. The onset of the transition is at 5.6 GPa. It involves a symmetry decrease. The low-pressure phase is described by space group P3̅m1 and the high-pressure phase by space group Pnma. For KSrPO4 and K2Ce(PO4)2, no evidence of phase transitions has been found up to the highest pressure covered by the experiments. For the three compounds, the linear compressibility for the different crystallographic axes and the pressure-volume equation of states are reported and compared with those of other phosphates. The three studied compounds are among the most compressible phosphates. The results of the study improve the knowledge about the high-pressure behavior of complex phosphates.

Novel application of sodium manganese oxide in removing acidic gases in ambient conditions.

In this study, we have demonstrated the application of sodium manganese oxide for the chemisorption of toxic acidic gases at room temperature. The fabricated alkali ceramic has Na0.4MnO2, Na2Mn3O7, and NaxMnO2 phases with a surface area of 2.6 m2 g-1. Na-Mn oxide was studied for oxidation of H2S, SO2, and NO2 gases in the concentration range of 100-500 ppm. The material exhibited a high uptake capacity of 7.13, 0.75, and 0.53 mmol g-1 for H2S, SO2, and NO2 in wet conditions, respectively. The material was reusable when regenerated simply by soaking the spent oxide in a NaOH-H2O2 solution. While the H2S chemisorption process was accompanied by sulfide, sulfur, and sulfate formation, the SO2 chemisorption process yielded only sulfate ions. The NO2 chemisorption process was accomplished by its conversion to nitrite and nitrate ions. Thus, the present work is one of the first reports on alkali ceramic utilization for room-temperature mineralization of acidic gases.

Fabrication of Na0.4MnO2 Microrods for Room-Temperature Oxidation of Sulfurous Gases.

Phase pure Na0.4MnO2 microrods crystallized in the orthorhombic symmetry were fabricated for the wet oxidation of H2S and SO2 gases at room temperature. The material was found highly effective for the mineralization of low concentrations of acidic gases. The material was fully regenerable after soaking in a basic H2O2 solution.

Structural Characterization of Aurophilic Gold(I) Iodide under High Pressure.

The effects of pressure on the crystal structure of aurophilic tetragonal gold iodide have been studied by means of powder X-ray diffraction up to 13.5 GPa. We found evidence of the onset of a phase transition at 1.5 GPa that is more significant from 3.8 GPa. The low- and high-pressure phases coexist up to 10.7 GPa. Beyond 10.7 GPa, an irreversible process of amorphization takes place. We determined the axial and bulk compressibility of the ambient-pressure tetragonal phase of gold iodide up to 3.3 GPa. This is extremely compressible with a bulk modulus of 18.1(8) GPa, being as soft as a rare gas, molecular solids, or organometallic compounds. Moreover, its response to pressure is anisotropic.