Research on the optical and EPR spectral data and the local structure for the trigonal Mn4+ centers in MgTiO3 crystal

- Optical and EPR data of trigonal Mn4+ centers in MgTiO3 are calculated.
- Diagonlization method based on the two-spin-orbit-parameter model is applied.
- Computed optical and EPR data agree reasonably with the observed values.
- Polar angular distortion of Mn4+ center in MgTiO3 is suggested.

The optical bands and EPR (or spin-Hamiltonian) parameters (g factors g//, g⊥ and zero-field splitting D) for Mn4+ ions at the trigonal octahedral Ti4+ site of MgTiO3 crystal are uniformly computed by virtue of the complete diagonalization (of energy matrix) method based on the two-spin-orbit-parameter model, where besides the effects of spin-orbit parameter of central dn ion on the spectral data (in the classical crystal field theory), those of ligands are also contained. The computed eight optical and EPR spectral data with four suitable adjustable parameters (note: differing from those in the previous work within cubic symmetry approximation where the used Racah parameters violate the nephelauxetic effect, the present Racah parameters obey the effect and hence are suitable) are rationally coincident with the experimental values. In particular, the calculated ground state splitting 2D, the first excited splitting ΔE(2E) and g-anisotropy Δg (=g//−g⊥) (they depend strongly on the angular distortion of d3 centers) are in excellent agreement with the observed values, suggesting that the angular distortions caused by the impurity-induced local lattice relaxation obtained from the above calculation for the trigonal Mn4+ impurity center in MgTiO3: Mn4+ crystal seem to be acceptable.

The optical and EPR data of trigonal Mn4+ center in MgTiO3 crystal are explained uniformly from the complete diagonlization method based on the two-spin-orbit-parameter model. The defect structure of Mn4+ center in MgTiO3 is also estimated.28