Large-magnitude high-spin nuclear parameters in a Ti3+ center from X-band EPR measurements at 10 K

Precise 10 K X-band EPR measurements and subsequent spin-Hamiltonian analysis by direct matrix diagonalization methods are reported for a Ti3+ (S = 1/2) center in tetragonal zircon (zirconium silicate, ZrSiO4). A special, and previously unobserved, feature of the supposedly uniaxial spectrum is the marked angular dependence of the titanium hyperfine lines in the perpendicular, ab crystal plane. As discussed, this can only arise from the presence of high-spin nuclear terms of dimension BIk, SIk (k = 3, 5) in the spin Hamiltonian. Parameters arising from these terms were determined to have magnitudes very much larger than observed previously in first-row transition ions. The consequences of precise determination of these high-spin parameters are significant and several: a precise determination of the nuclear quadrupole tensor leading to a ratio 47P/49P in excellent agreement with the ratio derived from the corresponding nuclear quadrupole moments; an apparent anisotropy in the nuclear Zeeman interaction which can be identified with anisotropy in the chemical shielding "tensor"; a marked hyperfine anomaly. The origin and significance of these observations are discussed.