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Magnetic resonance studies of (ReO4)2- in calcium tungstate

The e. p. r. spectrum of (ReO4)2– in CaWO4 has been measured in the temperature 4–120 K as a function of orientation. The spectrum including many forbidden lines may be fitted to the spin Hamiltonian H = μB B· g· S· + I· Ã· S. + I· P̃. I· in tetragonal form with S = ½ and I =5/2. At 4.2 K, endor measurements for the magnetic field oriented parallel to the unique axis, taken in conjunction with the e. p. r. spectrum, yield spin Hamiltonian parameters gǁ = 1.8549 ± 0.0002, g⊥ = 1.7164 ± 0.0002, Aǁ = ( ± )(42 ± 2) x 10-4cm-1, A⊥ = (±) (32 ± 2) x 10-4 cm-1 and P ǁ = (∓) (5 ± 3) x 10-4 cm-1, with gN = ( ± ) 1.27 for the 187Re nuclide. These parameters are consistent with the single electron occupying the |3z2 — r2> orbital of a 5d1 ion. The e. p. r. linewidth, which is strongly sensitive to both orientation and temperature, has been examined in detail. Preliminary studies of the relaxation properties of the centre are discussed in qualitative terms.