A systematic analysis of the spectra of trivalent actinide chlorides in D3h site symmetry

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Abstract
The optical spectra of actinide ions in the compound AnCl3 and doped into single‐crystal LaCl3 were interpreted in terms of transitions within 5fN configurations. Energy‐level calculations were carried out using an effective‐operator Hamiltonian, the parameters of which were determined by fitting experimental data. Atomic and crystal‐field matrices were diagonalized simultaneously assuming an approximate D3h site symmetry. Spectroscopic data were taken from the literature but in most cases supplemented by unpublished measurements in absorption and in fluorescence. Data for each ion were analyzed independently, then the model parameters were intercompared and in many cases adjusted such that in the final fitting process the principal interactions showed uniform trends in parameter values with increasing atomic number. Consistent with analyses of the spectra of lanthanide ions in both LaCl3 and LaF3, abrupt changes in magnitude of certain crystal‐field parameters were found near the center of the 5fN series. This resulted in two groups of parameter values, but with consistent trends for both halves of the series, and generally very good agreement between observed and computed energies. A new energy‐level chart based on computed crystal‐field level energies for each trivalent actinide ion has been prepared.

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