Optical properties of ZnCr2Se4 - Spin-phonon coupling and electronic d-d-like excitations

We studied the optical properties of antiferromagnetic ZnCr 2 Se 4 by infrared spectroscopy up to 28,000 cm -1 and for temperatures from 5 to 295 K. At the magnetic phase transition at 21 K, one of the four phonon modes reveals a clear splitting of 3 cm -1 as a result of spin-phonon coupling, the other three optical eigenmodes only show shifts of the eigenfrequencies. The antiferromagnetic ordering and the concomitant splitting of the phonon mode can be suppressed in a magnetic field of 7 T. At higher energies we observed a broad excitation band which is dominated by a two-peak-structure at about 18,000 cm -1 and 22,000 cm -1 , respectively. These energies are in good agreement with the expected spin-allowed crystal-field transitions of the Cr 3+ ions. The unexpected strength of these transitions with d - d character is attributed to a considerable hybridization of the selenium p with the chromium d orbitals.