Electronic Structure and Jahn-Teller Effect in GaN:Mn and ZnS:Cr

We present an ab initio and analytical study of the Jahn-Teller effect in two diluted magnetic semiconductors with d(4) impurities, namely Mn-doped GaN and Cr-doped ZnS. We show that the correct insulating electronic structure may be obtained by a proper treatment of the strong electron correlation in the 3d shell in combination with the Jahn-Teller distortion which breaks the local symmetry. Using the LSDA + U approach, we treat the zinc-blende and the wurtzite crystal structures of GaN:Mn, as well as zinc-blende ZnS:Cr. We show that the trigonal distortion due to the wurtzite structure is less important than the Jahn-Teller deformation. This observation allows us to construct a simplified phenomenological ligand field theory (trigonal influence is neglected) which completes the ab initio part. Our work corrects previous studies and the obtained energy gain due to the Jahn-Teller effect (from both the LSDA + U calculation and the ligand field theory) is in good agreement with the experimental data. The same is true for the complete set of crystal field parameters obtained from the phenomenological model which agrees well with previous optical measurements.