Abstract
A very detailed analysis of the fine structure of the 4E(G) state of Mn2+ in cubic and nearly cubic clusters is presented to account for the unusual fine structure observed in ZnSe:Mn. First, experimental results are reported which show that the spin-orbit interaction in the 4E(G) state of Mn2+ in ZnSe is about one half of that previously observed in cubic or nearly cubic clusters as MnS4, MnBr4, and MnCl4 and that the state Γ8 is neatly shifted with respect to the Kramers doublets Γ6 and Γ7. Second, a model is elaborated which shows that second-order spin-orbit interactions reduced by a Jahn–Teller coupling to E vibrational modes accounts well for the observed overall splitting of the 4E(G) state in the studied clusters and that fourth-order spin-orbit interactions correctly describe the shifts of the Γ8 state. The validity of the perturbation schemes is discussed and the results are compared to those obtained from a complete diagonalization in the d5 configuration.
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