We report high-resolution x-ray Raman scattering studies of high-order multipole spectra of rare earth 4d → 4f excitations (the N4,5 absorption edge) in nanoparticles of the phosphates LaPO4, CePO4, PrPO4, and NdPO4. We also present corresponding data for La 5p → 5d excitations (the O2,3 edge) in LaPO4. The results are compared with those from calculations by atomic multiplet theory and for the dipole contribution to the La 4d → 4f transition from a calculation using time-dependent density functional theory (TDLDA). Agreement with the atomic multiplet calculations for the high-order multiplet spectra is remarkable in the case of the N4,5 spectra. In contrast, we find that the shallow O2,3 semicore excitations in LaPO4 manifest a relatively broad band and an apparent quenching of 5p spin-orbit splitting. The more sophisticated TDLDA, which has earlier been found to explain dipolar spectra well in Ba compounds, is less satisfactory here in the case of La.
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CITATION STYLE
Huotari, S., Suljoti, E., Sahle, C. J., Rädel, S., Monaco, G., & De Groot, F. M. F. (2015). High-resolution nonresonant x-ray Raman scattering study on rare earth phosphate nanoparticles. New Journal of Physics, 17. https://doi.org/10.1088/1367-2630/17/4/043041