The Loewdin orthogonalization procedure being the well-known technique, particularly in quantum chemistry, however, gives rise to novel effects missed in earlier studies. Making use of the technique of irreducible tensorial operators we have develope
d a regular procedure for account of the orthogonalization effects. For illustration we address the emergence of a specific magnetoelectric coupling for noncentrosymmetric 3d or 4f ions.
Luminescence spectra of NiO have been investigated under vacuum ultraviolet (VUV) and soft X-ray (XUV) excitation. Photoluminescence (PL) spectra show broad emission bands centered at about 2.3 and 3.2 eV. The PL excitation (PLE) spectral evolution a
nd lifetime measurements reveal that two mechanisms with short and long decay times, attributed to the d($e_g$)-d($e_g$) and p($pi$)-d charge transfer (CT) transitions in the range 4-6,eV, respectively, are responsible for the observed emissions, while the most intensive p($sigma$)-d CT transition at 7,eV appears to be a weak if any PL excitation mechanism. The PLE spectra recorded in the 4-7,eV range agree with the RIXS and reflectance data. Making use of the XUV excitation allows us to avoid the predominant role of the surface effects in luminescence and reveal bulk luminescence with puzzling well isolated doublet of very narrow lines with close energies near 3.3,eV characteristic for recombination transitions in self-trapped emph{d}-emph{d} CT excitons formed by coupled Jahn-Teller Ni$^+$ and Ni$^{3+}$ centers. This conclusion is supported both by a comparative analysis of the luminescence spectra for NiO and solid solutions Ni$_{x}$Zn$_{1-x}$O, and by a comprehensive cluster model assignement of different emph{p}-emph{d} and emph{d}-emph{d} CT transitions, their relaxation channels. To the best of our knowledge it is the first observation of the self-trapping for emph{d}-emph{d} CT excitons. Our paper shows the time resolved luminescence measurements provide an instructive tool for elucidation of the emph{p}-emph{d} and emph{d}-emph{d} CT excitations and their relaxation in 3d oxides.
The incommensurate (IC) spin ordering in quasi-1D edge-shared cuprate NaCu_2O_2 has been studied by ^{23}Na nuclear magnetic resonance spectroscopy in an external magnetic field near 6 Tesla applied along the main crystallographic axes. The NMR lines
hape evolution above and below T_Napprox12 K yields a clear signature of an IC static modulation of the local magnetic field consistent with a Cu^{2+} spin spiral polarized in the bc-plane rather than in the ab-plane as reported from earlier neutron diffraction data.
