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EPR spectroscopic characterization of Gd/sup 3 +/ in the monazite-type rare-earth orthophosphates: LaPO/sub 4/, CePO/sub 4/, PrPO/sub 4/, NdPO/sub 4/, SmPO/sub 4/, and EuPO/sub 4/

Journal Article · · Phys. Rev. B: Condens. Matter; (United States)

The mineral monazite, a mixed lanthanide orthophosphate LnPO/sub 4/, is considered as a perfect host for geologic disposal of actinides, rare earths, and possibly other elements formed during nuclear-reactor operation. Synthetic monazite-type orthophosphates of all the elements of the first half of the lanthanide series (except Pm) have been prepared: single crystals were grown using a flux technique, and powders were precipitated in molten urea. The electron paramagnetic resonance (EPR) spectra of intentionally added Gd impurities show that the Gd/sup 3 +/ ions occupy predominantly substitutional rare-earth sites in both the flux-grown single crystals and the precipitated powders. Though these sites have a very low (triclinic C/sub 1/) symmetry, the spectra were successfully interpreted using an orthorhombic spin Hamiltonian. It has been found that, while the main spin-Hamiltonian parameter b/sup 0//sub 2/ is almost constant when going from the LaPO/sub 4/ to the EuPO/sub 4/ host (b/sup 0//sub 2/approx. =+830 x 10/sup -4/ cm/sup -1/), the parameter b/sup 2//sub 2/ decreases monotonically from +373 x 10/sup -4/ to +283 x 10/sup -4/ cm/sup -1/, respectively. The complete analysis (i.e., angular variations of the EPR lines and position of the principal electric-field axes relative to the crystallographic axes) of the EPR single-crystal spectra has been done for the two diamagnetic hosts LaPO/sub 4/ and EuPO/sub 4/, where the observed EPR lines are the sharpest. It is shown, in particular, that the two magnetically inequivalent EPR spectra (i.e., 14 lines) observed for the monazite-type single crystals are in fact equivalent when the magnetic field is applied parallel or perpendicular to the b axis of the monoclinic structure (i.e., for these directions, only seven degenerate lines are observed). These results are in perfect agreement with the description of the monazite structure.

Research Organization:
Solid State Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830
DOE Contract Number:
W-7405-ENG-26
OSTI ID:
6685912
Journal Information:
Phys. Rev. B: Condens. Matter; (United States), Journal Name: Phys. Rev. B: Condens. Matter; (United States) Vol. 23:3; ISSN PRBMD
Country of Publication:
United States
Language:
English