Optical absorption spectrum of dilute U4+ impurities in incommensurate ThBr4 : lineshape analysis

Crystal-field transitions associated with U4+ impurities diluted in ThBr4 give rise to broad absorption bands characterized by edge singularities. We show that the experimental spectra are consistent with the known occurrence of a sinusoidal distortion which modulates the Br- ion equilibrium positions, thus reducing the actinide site-symmetry from D2d to D2. The observation of spectral singularities corresponding to D2d-sites is interpreted as resulting from the partial pinning of the incommensurate modulation by the U4+ impurities

Absorption and emission spectra of U4 + diluted in the incommensurate structure of ThCl4

The absorption and fluorescence spectra of U4+ diluted in single crystals of ThCl4 have been measured at temperatures ranging from 4.2 K to room temperature. β-ThCl4 exhibits on incommensurate structure below 70 K with a loss of periodicity along the c axis. This results in a variation of the distance between the metal and the halogen from one cell to another. The site symmetry of the actinide ions is then reduced. The lines corresponding to the sites of the resulting symmetries S4 and D2 are identified spectroscopically. The S4 symmetry is approximated by the D2d one and a parametric analysis of the energy levels of U4 + in the D2d and D 2 symmetries is reported. For 25 levels in the D2d site the root mean square deviation σ is 46 cm-1 and for 34 levels in D2, σ = 56 cm-1. The parameters which occur in both symmetries are only slightly changed

Spectroscopic study of the incommensurate phase of ThBr4 via the optical and magnetooptical properties of U4+

U4+ is used to probe the incommensurate structure of ThBr 4 via absorption and magnetic circular dichroism (MCD) measurements. Below Tc = 95 K, the crystal field experienced by U 4+ ions is either of D2d or D2 symmetry. This can be simulated by varying a phase angle ϕ form 0(D 2d) to ± π/2 (D2). One very neat advantage of MCD over absorption is that the D2d centres show up very clearly in the former due to the occurrence of a derivative-like singularity. We present a model to simulate absorption, Zeeman and MCD profiles. It accounts satisfactorily for most of our data and we arrive at the following main conclusions : (i) it is probable that the phase is truly incommensurate since the lower limit of the number of sites is found to be 80; (ii) for a low concentration of U4+ (2 x 10-4), we found no evidence of a pinning of the incommensurate modulation by the impurities. MCD provides also a definite proof that the ground state of U 4+ in ThBr4 is Γ4 with a D2 d symmetry. Finally, we determine the Landé factors of five excited states, our findings being in fair agreement with the results of recent crystal field calculations

Propriétés spectroscopiques de U4+ dans ThBr4

L'indexation de raies à zéro phonon du spectre d'absorption de ThBr4 : U4+ est discutée, compte tenu du spectre de vibration de la matrice et des spectres d'émission de ces monocristaux excites par laser

Spectroscopie optique de l’uranium tétravalent dans les phases incommensurables

Les phases incommensurables de ThBr4 et ThCl4 modulent, à basse température, les propriétés d’absorption et de fluorescence de l’ion U4+ introduit comme dopant dans ces matrices