Single-crystal EPR studies of transition-metal ions in inorganic crystals at very high frequency

Electron paramagnetic resonance (EPR) single-crystal rotation studies at very high frequency (249.9 GHz) of transition metal ions with electron spins greater than one-half are reported. At 249.9 GHz, the spectra are in the high-field limit despite large zero-field splittings. This leads to a considerable simplification of the spectra, and aids in their interpretation. Single-crystal 249.9 GHz EPR spectra of Ni²⁺ in Ni₂CdCl₆· 12H₂O, Mn²⁺ (0.2%) in ZnV₂O₇, and Fe³⁺ (2%) in CaYA10₄ were recorded at 253 K in an external magnetic field of up to 9.2 T, along with those at X-band and Q-band frequencies at 295 K and lower temperatures. The goniometer used at 249.9 GHz for single-crystal rotation is based on a quasi-optical design and is an integral part of a special Fabry-Pérot resonator. The values of the spin-Hamiltonian parameters were estimated from a simultaneous fitting of all of the observed line positions at several microwave frequencies recorded at various orientations of each crystal with respect to the external magnetic field with least-squares fitting in conjunction with matrix diagonalization. Estimates of zero-field splitting parameterD at room temperature are: for Ni²⁺, about ?31 GHz (site I) and about ?7 GHz (site II); for Mn²⁺, about 6 GHz; and for Fe³⁺, about 29 GHz.