Wydział Chemii

Mirosław Karbowiak

Janusz Drożdżyński

2004

Journal of Solid State Chemistry

177

2415-2422

10.1016/S0022-4596(03)00394-3

Naukowa

Angielski

Artykuł

Temperature-dependent line broadening measurements of emission and excitation transitions for two intrinsic sites U(1) and U(2) of U³⁺ ions doped in a RbY₂Cl₇ single crystals as well as of U⁴⁺ ions have been performed. Values of the electron phonon (EP) coupling parameter were determined by a fit of experimentally observed line widths to an equation containing the temperature dependent broadening term due to the Raman two-phonon process. The parameters for U³⁺ ions in RbY₂Cl₇ are larger than those determined for this ion in LaCl₃ host crystals. This is due to shorter M–Cl distances in RbY₂Cl₇ which leads to a stronger interaction of uranium with the chlorine ions and to an increase of covalency. The relatively large value determined for the multiplet of U³⁺ in RbY₂Cl₇ may result from the proximity of opposite parity 5f²6d¹ states. The parameters obtained for the U³⁺ ions are larger than those for U⁴⁺. The latter ones are affected by a stronger crystal-field (CF), however the position of the first 5f²6d¹ or 5f¹6d¹ states, which for U³⁺ is observed at an energy of ∼15,000 cm⁻¹ lower than for U⁴⁺, is the dominating one among the factors influencing the EP coupling strength. The EP coupling parameters for all investigated transitions of the U³⁺ ions are larger for U(2) than for U(1), which results mainly from the larger crystal field strength observed for the U(2) site. The differences in the EP coupling strength of the U³⁺ ions in the U(1) and U(2) sites are in accordance with decay times observed for emission for both sites from the multiplet.

https://doi.org/10.1016/S0022-4596(03)00394-3

http://www.elsevier.com