Two-photon spectroscopy of samarium(III) in the elpasolite Cs₂NaYCl₆:Sm³⁺

Abstract

We present polarized two-photon excitation (TPE) spectra for samarium(III) f 5 in the elpasolite Cs 2 NaYCl 6 . Approximately 80 levels have been assigned up to 29 000 cm −1 with the aid of a one-electron crystal field Hamiltonian, representing the most complete and extensive data set so far reported for Sm(III) at a cubic site. Deviations from the predictions of one-electron theory are discussed in terms of the spin correlated crystal field (SCCF).

Energy levels of terbium(III) in the elpasolite Cs2NaTbBr6. II. A correlation crystal field analysis

“…For practical reasons then, the TPA spectra of ions such as Sm(II1) [31], Eu(II1) [32], Gd(II1) [33], Tb(II1) [23,24] and Dy(III), provide access to an unusually large set of level assignments. Their analysis is only feasible in cubic sites, whose symmetry minimizes the number of ligand field parameters.…”

Electronic Energy Levels and Optical Transitions in Samarium(III) Solvates

“…We have been interested in the fundamental optical properties in solution, − while others have focused on developing lanthanide luminescence-based bioimaging and bioassay. − Most of the work has focused on europium-centered luminescence, ,, while some very elegant work has been done with samarium­(III). ,− Electronic energy levels and optical spectra of samarium­(III) in crystals have previously been studied in detail, − but we have not been able to find modern literature describing the fundamental properties of this particular lanthanide­(III) ion in solvates. , Thus, we set out to investigate the electronic energy levels and optical transitions in samarium­(III) solvates following the methodology we developed in similar works on dysprosium­(III) and ytterbium­(III) inspired by the methodologies of similar publications. ,,− …”

Electronic Spectra and Configuration Interaction of Tm3+ in TmCl63-

“…Several systematic energy level parametrizations have been carried out for the entire series of lanthanide ions with general overall success, but with some notable discrepancies. − Although the SL -term-dependence of the crystal field parameters has been recognized for some time, attempts to explain “anomalous” multiplet splittings using two-electron operators have not proved to be conclusive. , More recent parametrizations have utilized larger datasets, including energy levels deduced from two-photon spectroscopy. Evidence was reported for electron correlation induced by the crystal field, yet until recently the comparisons of experimental versus calculated energy level listings have been those from calculations involving one-electron crystal field operators. − A recent paper by Thorne et al shows that improvement can be obtained by adding the spin-correlated crystal field to the normal crystal field. Some discrepancies remain, however, and a detailed account of correlation crystal field analysis for Cs 2 NaTbBr 6 is given in ref .…”

“…Evidence was reported for electron correlation induced by the crystal field, 7 yet until recently the comparisons of experimental versus calculated energy level listings have been those from calculations involving one-electron crystal field operators. [8][9][10][11][12] A recent paper by Thorne et al 13 shows that improvement can be obtained by adding the spin-correlated crystal field to the normal crystal field. Some discrepancies remain, however, and a detailed account of correlation crystal field analysis for Cs 2 NaTbBr 6 is given in ref 14.…”