Jahn-Teller effect in the emission and absorption spectra of ZnS:Cr ²⁺ and ZnSe:Cr²⁺

The Jahn-Teller effect is invoked to explain the fine structure (isolated zero-phonon lines) observed in both the infrared emission and absorption spectra of substitutional Cr²⁺ impurities in ZnSe and ZnS. The ground ⁵D₂ term of Cr²⁺ is split by crystal field into a ⁵F₂ ground multiplet and an excited ⁵E multiplet. We look at transitions among levels belonging to these two multiplets, which happen to be in the near infrared region. Spin-orbit and spin-spin interactions are taken into account. The Jahn-Teller coupling is introduced as a linear coupling considering both e and T₂ phonons. The Lanczos-recursion procedure with a proper choice of the initial state is used to calculate the vibronic functions and energies. It is found that e modes only lead to intensities that do not agree well with those of the zero-phonon doublet observed both in emission and absorption in the cases of ZnS and ZnSe, while τ₂ modes give a good explanation of transition energies and transitions strengths in the same cases. A discussion of the relatively high strength of the vibronic coupling for Cr in comparison with other impurities in the same compounds is also included.