A systematic analysis of the spectra of trivalent actinide chlorides in D sub 3 h site symmetry

Journal Article · Mon Jun 15 04:00:00 EDT 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.462278· OSTI ID:7305776

Carnall, W T ^[1]

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1. Argonne National Laboratory, Argonne, Illinois 60439 (United States)

The optical spectra of actinide ions in the compound AnCl{sub 3} and doped into single-crystal LaCl{sub 3} were interpreted in terms of transitions within 5{ital f}{sup {ital N}} 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 {ital D}{sub 3{ital h}} 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 Spectroscopic data were taken from the literature but in most cases supplemented by unpublished measurements in absorption and in fluorescence.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 LaCl{sub 3} and LaF{sub 3}, abrupt changes in magnitude of certain crystal-field parameters were found near the center of the 5{ital f}{sup {ital N}} 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.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 7305776
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 96:12; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360606* -- Other Materials-- Physical Properties-- (1992-)
ABSORPTION
ACTINIDE COMPOUNDS
ACTINIUM CHLORIDES
ACTINIUM COMPOUNDS
CATIONS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
CRYSTAL DOPING
CRYSTAL FIELD
CRYSTALS
ENERGY LEVELS
FLUORESCENCE
HALIDES
HALOGEN COMPOUNDS
HAMILTONIANS
IONS
LANTHANUM CHLORIDES
LANTHANUM COMPOUNDS
LUMINESCENCE
MATHEMATICAL OPERATORS
MATRIX ISOLATION
MONOCRYSTALS
OPTICAL PROPERTIES
PHYSICAL PROPERTIES
QUANTUM OPERATORS
RARE EARTH COMPOUNDS
RESOLUTION
SORPTION
TEMPERATURE RANGE
TEMPERATURE RANGE 0000-0013 K
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K