The optical orientation of Mn$^{ 2+}$ spins in the first excited state $^4$T$_1$ was experimentally observed in bulk (Zn, Mn)Se ($x_\mathrm{ Mn}=0.01$) in the an external magnetic field of up to $6\,$T in Faraday geometry. This occurred during quasi-resonant continuous wave circularly polarized photoexcitation of the intracenter d-d transitions. A non-monotonic dependence of the thermal circular polarization of the intracenter photoluminescence on the magnetic field was observed. A theoretical model is proposed to describe the selection rules for resonant optical d-d transitions of an isolated Mn$^{ 2+}$ ion in a ZnSe cubic crystal. These rules are based on the analysis of the total angular momentum symmetry for the ground ($^6$A$_1$) and first excited ($^4$T$_1$) states of the Mn$^{ 2+}$ ion. This discussion neglects the specific mechanism for spin-flip processes in a d-shell of the ion during optical excitation. The analysis is founded on the rotational symmetry of the effective total angular momenta and parity for each state as a whole. Additionally, the Jahn-Teller coupling of the excited state orbital parts with tetragonal ($e$-type) local distortions of the crystal lattice is considered. This coupling results in the segregation of cubic axes and spin projections on these axes due to weak spin-orbit and spin-spin coupling in the excited state. This leads to energy splitting for spin states with their projections of $\pm 1/2$ and $\pm 3/2$ on each axis distinguished by specific Jahn-Teller distortion in the corresponding atomic potential minimum. By introducing two different times of relaxation to reach thermodynamic equilibrium for $\pm 1/2$ and $\pm 3/2$ states in each Jahn-Teller configuration, an angle dependent optical orientation contribution in photoluminescence polarization arises in the presence of a magnetic field.
Categories: cond-mat.mes-hall cond-mat.mtrl-sci