RESUMO
The defect models of the orthorhombical and tetragonal Cu2+ centers in Pb[Zr0.54Ti0.46]O3 are attributed to Cu2+ ions occupying the sixfold coordinated octahedral Ti4+ site with and without charge compensation, respectively. The electron paramagnetic resonance (EPR) g factors gi (i = x, y, z) of the Cu2+ centers in Pb[Zr0.54Ti0.46]O3 are theoretically studied by using the perturbation formulas of a 3d9 ion under orthorhombically and tetragonally elongated octahedra. Based on the calculation, the impurity off-center displacements are about 0.253 and 0.162 Å for the orthorhombical and tetragonal Cu2+ centers, respectively. Meanwhile, the planar Cu2+-O2- bonds are found to experience the relative variation ΔR (≈0.102 Å) along the a- and b-axes for the orthorhombical Cu2+ center due to the Jahn-Teller (JT) effect. The theoretical EPR g factors based on the above local structures agree well with the observed values.
RESUMO
The local structure and spin Hamiltonian parameters (SHPs) g factors (gx , gy , gz ) and the hyperfine structure constants (Ax , Ay , Az ) for Cu2+ doped in the LiTaO3 crystal are theoretically investigated by the perturbation formulas for a 3d9 ion under rhombically elongated octahedral based on the cluster approach. The impurity Cu2+ was assumed to occupy the host trigonally-distorted octahedral Li+ site and experience the Jahn-Teller (JT) distortion from the host trigonal octahedral [TaO6 ]10- to the impurity rhombically elongated octahedral [CuO6 ]10- . Based on the calculations, the impurity-ligand bond lengths parallel and perpendicular to the C2 -axis are found to be R|| (≈ 2.305 Å) and R⥠(≈ 2.112 Å) for the studied [CuO6 ]10- cluster, with the planar bond angle θ (≈ 78.2°). Meanwhile, the ground-state wave function for Cu2+ center in LiTaO3 was also obtained. The calculated SHPs based on the above local lattice distortions agree well with the experimental data, and the results are discussed.