The three sets of crystal field parameters （CFPs） obtained from spectroscopic and magnetic susceptibility studies of Tb3＋（4f^8） ions in TbAlO3 by Gruber et al. （J. Lumin. 128 （2008） 1271） were reanalyzed. The...The three sets of crystal field parameters （CFPs） obtained from spectroscopic and magnetic susceptibility studies of Tb3＋（4f^8） ions in TbAlO3 by Gruber et al. （J. Lumin. 128 （2008） 1271） were reanalyzed. These sets, fitted from experimental energy levels, are physically equivalent and correspond to specific choices of the axis system. Proper interpretation of experimental data for Tb3＋ ions at monoclinic C8 symmetry sites in TbAlO3 crystal requires clarification of several intricate low syrmnetry aspects, namely, （a） three equivalent forms of monoclinic CF Hamiltouian, （b） relative orientation of the crystallographic axis system w.r.t, the symmetry-adapted axis system, （c） monoclinic standardization of CFPs, （d） distinction between the actual and apparent low symmetry effects exhibited by CFPs, and （e） nominal nature of all fitted CFP sets. For this purpose, modeling of CFPs for Tb3＋ in TbAlO3 was carried out using at the first stage only the Coulomb, i.e. point charge, eonlribntions in the exchange charge model. The point charge model calculated CFPs disagree with the experimental CFPs, especially the rank k=6 CFPs. To explain this discrepancy and to verify the correcmess of the theoretical CFP calculations additionally the superposition model was employed. The methods of analysis and modeling of CFP sets for monoclinic symmetry cases proposed here proved useful for the studied case as well as might be used for other ion-host systems exhibiting monoclinic or triclinic local site symmetry. Partial results for Tb3＋ ions in TbAlO3 were presented here, whereas detailed results were given in a follow-up paper.展开更多
Detailed spectroscopic studies of Pr3＋ ions in BiBO glass and Ca4GdO（BO3）3 crystal were performed. Experimental absorption spectra were measured at room temperature and assigned. The first principles discrete varia...Detailed spectroscopic studies of Pr3＋ ions in BiBO glass and Ca4GdO（BO3）3 crystal were performed. Experimental absorption spectra were measured at room temperature and assigned. The first principles discrete variational multielectron method was used to model the polarized absorption spectra of the Ca2GdO（BO3）3：Pr3＋; without any fitting parameters, the overall appearance of the spectra was reproduced satisfactorily. The energy intervals between different molecular orbitals in the [PrO6] cluster were estimated. The conventional Judd-Ofelt theory was used to calculate the oscillator strengths of the 4f-4f transitions in the BiBO：Pr3＋ system; the set of the phenomenological intensity parameters was determined.展开更多
基金supported by the research grant from the Polish Ministry of Science and Tertiary Education in the years 2006-2009
文摘The three sets of crystal field parameters （CFPs） obtained from spectroscopic and magnetic susceptibility studies of Tb3＋（4f^8） ions in TbAlO3 by Gruber et al. （J. Lumin. 128 （2008） 1271） were reanalyzed. These sets, fitted from experimental energy levels, are physically equivalent and correspond to specific choices of the axis system. Proper interpretation of experimental data for Tb3＋ ions at monoclinic C8 symmetry sites in TbAlO3 crystal requires clarification of several intricate low syrmnetry aspects, namely, （a） three equivalent forms of monoclinic CF Hamiltouian, （b） relative orientation of the crystallographic axis system w.r.t, the symmetry-adapted axis system, （c） monoclinic standardization of CFPs, （d） distinction between the actual and apparent low symmetry effects exhibited by CFPs, and （e） nominal nature of all fitted CFP sets. For this purpose, modeling of CFPs for Tb3＋ in TbAlO3 was carried out using at the first stage only the Coulomb, i.e. point charge, eonlribntions in the exchange charge model. The point charge model calculated CFPs disagree with the experimental CFPs, especially the rank k=6 CFPs. To explain this discrepancy and to verify the correcmess of the theoretical CFP calculations additionally the superposition model was employed. The methods of analysis and modeling of CFP sets for monoclinic symmetry cases proposed here proved useful for the studied case as well as might be used for other ion-host systems exhibiting monoclinic or triclinic local site symmetry. Partial results for Tb3＋ ions in TbAlO3 were presented here, whereas detailed results were given in a follow-up paper.
基金supported by the Polish Ministry of Science and Higher Education (POIG. 01.03, 01-14-016/08)
文摘Detailed spectroscopic studies of Pr3＋ ions in BiBO glass and Ca4GdO（BO3）3 crystal were performed. Experimental absorption spectra were measured at room temperature and assigned. The first principles discrete variational multielectron method was used to model the polarized absorption spectra of the Ca2GdO（BO3）3：Pr3＋; without any fitting parameters, the overall appearance of the spectra was reproduced satisfactorily. The energy intervals between different molecular orbitals in the [PrO6] cluster were estimated. The conventional Judd-Ofelt theory was used to calculate the oscillator strengths of the 4f-4f transitions in the BiBO：Pr3＋ system; the set of the phenomenological intensity parameters was determined.
