Fe K-edge x-ray magnetic circular dichroism of magnetite (Fe3O4) powders was measured with synchrotron radiation under variable pressure and temperature conditions in diamond anvil cell. The magnetic dichroism was observed to decrease discontinuously by approximately 50% between 12 and 16 GPa, independent of temperature. The magnetic transition is attributed to a high-spin to intermediate-spin transition of Fe2+ ions in the octahedral sites and could account for previously observed structural and electrical anomalies in magnetite at this pressure range. The interpretation of x-ray magnetic circular dichroism data is supported by x-ray emission spectroscopy and theoretical cluster calculations.

The structural, magnetic, electrical, and dilatation properties of the rare-earth NdCoO3 and SmCoO3 cobaltites were investigated. Their comparative analysis was carried out and the effect of multiplicity fluctuations on physical properties of the studied cobaltites was considered. Correlations between the spin state change of cobalt ions and the temperature dependence anomalies of the lattice parameters, magnetic susceptibility, volume thermal expansion coefficient, and electrical resistance have been revealed. A comparison of the results with well-studied GdCoO3 allows one to single out both the general tendencies inherent in all rare-earth cobaltites taking into account the lanthanide contraction and peculiar properties of the samples containing Nd and Sm.

Within the framework of a realistic multiband p-d model, we derived an effective Hamiltonian to describe the exchange interaction effects near the spin crossover in magnetic Mott-Hubbard insulators under pressure. It is shown that the single-ion mechanism of spin crossover under the change in the crystal field does not lead to a thermodynamic phase transition; however, at T = 0 a quantum phase transition appears. It has been found that the cooperativity leads to a modification of the quantum phase transition to a first-order phase transition and the appearance of metastable states of the system. The pressure-temperature phase diagram has been obtained to describe the magnetization and high-spin population near the spin crossover of Mott's insulators with d 6 ions.