Optical properties of manganese-doped yttrium orthoaluminate crystals (Mn:YAlO 3 ), grown by the Czochralski technique, are reported. Luminescence and absorption spectra indicate the presence of Mn 4ϩ ions in as-grown crystals, and Mn 3ϩ , Mn 4ϩ , and Mn 5ϩ ions simultaneously in photoexcited crystals. A permanent diffraction grating, erasable by heating, was obtained in the crystals with diffraction efficiency of more than 50% at 514.5 nm reading wavelength and 1-2 % in 632-930 nm wavelength range. Reading at wavelengths longer than 630 nm did not damage the recorded grating. The electro-optical effect observed in the photoexcited crystals implies that manganese ions disturb the YAlO 3 crystal structure so that it becomes noncentrosymmetric.

Solar fuels research aims to mimic photosynthesis and devise integrated systems that can capture, convert, and store solar energy in the form of high-energy molecular bonds. Molecular hydrogen is generally considered an ideal solar fuel as its combustion is essentially pollution-free. Cobaloximes rank among the most promising earth-abundant catalysts for the reduction of protons to molecular hydrogen. We have used multifrequency EPR spectroscopy at X-band, Q-band, and D-band combined with DFT calculations to reveal electronic structure and establish correlations between structure, surroundings and catalytic activity of these complexes. To assess the strength and nature of ligand cobalt interactions, the BF2-capped cobaloxime, Co(dmgBF2)2, was studied in a variety of different solvents with a range of polarities and stoichiometric amounts of potential ligands to the cobalt ion. This allows the differentiation of labile and strongly coordinating axial ligands for the Co(II) complex. Labile, or weakly coordinating, ligands like methanol result in larger g-tensor anisotropy than strongly coordinating ligands like pyridine. Additionally, a coordination number effect is seen for the strongly coordinating ligands with both singly-ligated LCo(dmgBF2)2 and doubly-ligated L2Co(dmgBF2)2. The presence of two strongly coordinating axial ligands leads to the smallest g-tensor anisotropy. The relevance of the strength of the axial ligand(s) to the catalytic efficiency of Co(dmgBF2)2 is discussed. Finally, the influence of molecular oxygen and formation of Co(III) superoxide radicals LCo(dmgBF2)2O2• is studied. The experimental results are compared with a comprehensive set of DFT calculations on Co(dmgBF2)2 model systems with various axial ligands. Comparison with experimental values for the “key” magnetic parameters like g-tensor and 59Co hyperfine coupling tensor allows the determination of the conformation of the axially ligated Co(dmgBF2)2 complexes. The data presented here are vital for understanding the influence of solvent and ligand coordination on the catalytic efficiency of cobaloximes.

In order to better understand the transition from quantum to classical behavior in spin system, electron magnetic resonance (EMR) is studied in suspensions of superparamagnetic magnetite nanoparticles with an average diameter of ~ 9 nm and analyzed in comparison with the results obtained in the maghemite particles of smaller size (~ 5 nm). It is shown that both types of particles demonstrate common EMR behavior, including special features such as the temperature-dependent narrow spectral component and multiple-quantum transitions. These features are common for small quantum systems and not expected in classical case. The relative intensity of these signals rapidly decreases with cooling or increase of particle size, marking gradual transition to the classical FMR behavior.

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We report on the integration of epitaxial colossal magnetoresistive La0.67Ba0.33MnO films on Si(100) semiconductor using SrTiO3 template layer by pulsed-laser deposition. X-ray diffraction reveals the superior quality of the manganite film that grows epitaxially on heteroepitaxially grown SrTiO3 template layer on Si substrate. The epitaxial films demonstrate remarkable surface morphology, magnetic transition and hysteresis, magnetoresistance, and ferromagnetic resonance, illustrating the ferromagnetic nature of the film and possible device applications at room temperature.