LAUSR

Abstract Systematic analysis of fine structure of the whole energy levels and spin-Hamiltonian parameters (zero-field splitting (ZFS) parameter D and g-factors g // and g ⊥ ) for the ground state 3 A 2 ( 3 T 1 ) of V 3+ ion in corundum are presented in detail with complete diagonalization method (CDM) of 45 × 45 energy matrix, in which the full configuration interactions are taken into account. The reduction of the splittings of excited electronic 3 T 2 (t 2 g e) term with orbital triplet degenerate caused by spin-orbit (SO) and lower trigonal crystal field (CF) is studied by T 2 ⊗ e model dynamic Jahn-Teller theory, and Ham deduction factor, the Jahn-Teller energy E JT and Huang-Rhys factor S are estimated. The studies are performed within the strong-field scheme with molecular orbit (MO) approximation, in which the two SO coupling parameter model is used and the SO contributions from both the central 3 d ion and ligands are taken in account. The calculated results are in good agreement with the experimental data, and the local structure of [VO 6 ] 9- cluster with C 3 point group symmetry are determined quantitatively.