Electronic spectra of 3d(n) transition ions in an octahedral ligand surrounding have been studied using the modified crystal field approach (MCFA), which includes a relativistic spin-orbital interaction. A new variable parameter, the effective nuclear charge Z(eff) of a metal ion that allows accounting implicitly the covalence degree of a metal-ligand bond, has been introduced. Energy diagrams similar to the Tanabe-Sugano ones have been calculated. To study the spin state evolution of the metal ion in an arbitrary distorted octahedral complex, a spin state diagram approach has been proposed. The intermediate-spin (IS) state problem for 3d(4), 3d(5), and 3d(6) metal ions has been considered and conditions for the IS state realization have been formulated. The regions of the mixed high-, intermediate-, and low-spin states have been found. The possibility of coexistence of the different spin states of 3d ions in the octahedral complexes has been considered using crystallography data for the YBaCo(2)O(5.5) layered cobaltite.

Quantitative description of charge transport across tunneling and break-junction devices with novel superconductors encounters some problems not present or not as severe for traditional superconducting materials. In this work, we explain unexpected features in related transport characteristics as an effect of a degraded nanoscaled sheath at the superconductor surface. A model capturing the main aspects of the ballistic charge transport across hybrid superconducting structures with normally conducting nanometer-thick interlayers is proposed. The calculations are based on a scattering formalism taking into account Andreev electron-into-hole (and inverse) reflections at normal metal-superconductor interfaces as well as transmission and backscattering events in insulating barriers between the electrodes. Current-voltage characteristics of such devices exhibit a rich diversity of anomalous (from the viewpoint of the standard theory) features, in particular shift of differential-conductance maxima at gap voltages to lower positions and appearance of well-defined dips instead expected coherence peaks. We compare our results with related experimental data.

Spin state (SS) transitions in metal-containing pyramidal complexes that originate from crystallographic distortions are the research subject of this work. The transition elements are considered to be in the 3d6 configuration (Fe2+, Co3+), and they display three different SSs: low-spin (LS,S = 0), intermediate-spin (IS,S = 1) and high-spin (HS,S = 2) states. They have been studied in the frame of the crystal field approximation via the effective nuclear charge Zeff and under oxygen cage distortions. The features of the SS stability have been calculated with/without accounting for spin–orbit coupling. Some critical points at which an accidental degeneracy of the SSs exist have been revealed. Near the critical points, negligible distortions can crucially change the SS. It is demonstrated that the ground SS of the pyramidal MeO5 complex is very sensitive to the symmetry and magnitude of its distortions. SS diagrams in the parameter space ‘effective charge’–‘distortion magnitude’ have been established. It is revealed that the IS state exists as a ground state for all considered distortions with a corresponding choice of Zeff. Jahn–Teller distortions stabilize the IS state in a wide range of Zeff. The orbital-like reorientation of the electron density distribution was observed for the IS state at some threshold magnitude of Jahn–Teller distortions.

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