Abstract
A model of one-electron states is devised to describe within the strong-field limit the chromium states Cr 2+(d 4) and Cr +(d 5) in tetrahedral crystal fields. The proposed advancement is the inclusion of spin-correlation effects, i.e. a differentiation between the energies of spin-up and spin-down electron configurations. The method comprises the known spin-allowed 5E(D)⇆ 5T 2(D) transitions of Cr 2+ and, above all, spin-forbidden transitions. The 4T 1(G)→ 6A 1(S) luminescence of ZnSe:Cr + peaking near v=10 300 cm −1 is interpreted as a t 2↓→e ↑ transition of the d 5 configuration. A weak emission band of ZnSe:Cr peaking near 6100 cm − at cryo-temperatures and its analogues in ZnS and other II–VI materials are now assigned to the t 2↑t 2↓e ↑ 2→t 2↑ 2e ↑ 2 spin-flip process of the Cr 2+ (d 4) configuration whose Jahn-Teller-stabilised ground state had earlier been proved to participate in this luminescence. The described emission bands provide for the first time direct means to derive from an experiment the spin-flip energy within the one-electron limit.
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