4f6→4f55d1absorption spectrum analysis ofSm

Abstract

The 4f 6 → 4f 5 5d 1 absorption spectrum of the Sm 2+ ions incorporated in a SrCl 2 single crystal was recorded at 4.2 K in the 15 000-45 000 cm −1 spectral range. The overall spectrum is very satisfactorily simulated by theoretical calculations performed in the frame of the semi-empirical Hamiltonian model. The calculations enabled the assignment of all bands observed in the spectrum as well as a prediction of some experimentally unobserved transitions in the 45 000-55 000 cm −1 region. The rich vibronic structure observed for absorption bands in the 15 000-25 000 cm −1 spectral region is dominated by the vibronic progressions in the totally symmetric Sr-Cl stretching mode of ϳ213 cm −1 upon the thirteen zero phonon lines and local vibration modes at ϳ81 cm −1 and ϳ116 cm −1 . This multiphonon vibronic spectrum is very well reproduced by the model calculation.

Sm2+ fluorescence and absorption in cubic BaCl2: Strong thermal crossover of fluorescence between 4f6 and 4f55d1 configurations

“…3. There is a very close similarity between the absorption spectra for LSCBC:Sm 2 þ and cubic SrCl 2 :Sm 2þ as reported by Karbowiak et al [17], which suggests that in LSCBC the predominant site is also of cubic or near cubic symmetry. The only band which is not common is the broad band evident in both absorption and excitation spectra at $ 41,000 cm À 1 which must arise from a different electronic centre.…”

“…The absorption comprises strong Sm 2þ absorption bands, but superposed on a rising background which is not observed for the similar cubic SrCl 2 :Sm system [17]. The background is not evident in the excitation spectra, and is not correlated with samarium concentration, so is probably not associated with the divalent samarium.…”

Transient photoluminescence enhancement as a probe of the structure of impurity-trapped excitons in CaF2:Yb2+

“…[4][5][6][7][8] Modern ab initio methods 9,10 are capable of accurately calculating excited-state electronic structure and bond-length variations, giving good agreement with available broad-band 4f N ↔ 4f N−1 5d spectra. The ab initio calculations 10 indicate that transitions between the excited states would give a combination of sharp-line and broad vibronic transitions.…”

“…7,10 The calculation is approximate because it uses an effective phonon frequency. A frequency of 325 cm…”

Spectroscopy of High‐Energy States of Lanthanide Ions

“…Detailed analyis of the vibrational spectrum for transitions that do change bond length, such as in Refs. [38,39] will give information about changes in excited state geometry.…”